1699

Index

a acrylate 199, 1612 abiraterone 426 – derivatives 1115, 1117 abnormal lactone (AL) 1495, 1496 – esters, synthesis of 1610 π-acceptors 828 acrylic acid 126, 1612

– π*-acceptor 810 – based on CO2 1610 – ligand 960 – thermodynamic situation 1611 accessible molecular surface (AMS) 834 acrylonitrile-butadiene-polystyrene acenaphthene imine derivative ligands 257 microencapsulated Os 1514 acetaldehyde 508 actinides 1071 – from ethylene 500 activated carbon 1343 – oxidation 95 activation energy 963 acetamide, transamidation of activation reaction 233 – amino acid catalyzed 1436 active catalyst system 283 acetic acid 93, 709, 1526 active noble metal complexes, reoxidation – nickel-based catalysts 105 1264 acetic anhydride 110, 111 acyclic diene metathesis polymerization 2´-acetonaphthone 735 (ADMET) 824 acetonitrile 708, 1547 acyclic ketones, BV oxidation of 1502 acetophenones 726, 730, 732, 734, 738, 1047 acyclic precursors 1343 – derivatives 726 N-acyl-α-amino acid derivatives acetylcholinesterase (AChE) inhibitor 1496 – synthesis 1197 acetylide ligand acylamidines 1469

– on photocatalytic H2 production 1668 N-acyl amino acids 1535 N-acetylmannosamine (ManNAc) 920 acylases 913 (+)-achalensolide, asymmetric synthesis 1300 N-acyl cyclic amines 1535 acid–amine coupling 1429 acyl hydrazones, with Rh/duphos 633 – boron derivative 1429 acyl ligand 103 acid–base interactions 860 acyl palladium complex 169 acid halides 525 acylphosphite 838 acidic hydrogen ion 492 1-adamantanol 1533 π-acidic ligands 1404 adapalene 429 acidic phosphate electrolyte, electrochemical adenine-thymine (A-T) 858 properties 1142 adiabatic flash 100 acids, promotor effect 1268 adipic acid Acinetobacter calcoaceticus 908 – fermentation of 1617 – NCIMB 9871 909 – production from LA 1629 acridine-based bisphosphine ligand 1629 aerobic oxidation 1057 acrolein acetal, Heck arylation of 974 Ag/Al2O3 catalyst 1445 acrolein, arylation 974 alcohol dehydrogenase (ADH) 901, 903

Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Four Volumes, Third Edition. Edited by Boy Cornils, Wolfgang A. Herrmann, Matthias Beller, and Rocco Paciello.  2018 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2018 by Wiley-VCH Verlag GmbH & Co. KGaA. 1700 Index

alcohols – Fe-catalyzed one-pot oxidative – alcohol/ketone (A/K) ratio 711 cleavage 1645 – oxidation 717, 720 – hydroamination of 1389, 1403 – oxidative carbonylation of 150 – hydroformylation reaction 1198, 1561 – primary alcohols 453 – hydroxycarbonylation of 1563 – secondary alcohols 1058, 1533 – insertion 970, 973 alcoholysis 1262 – isomerization 1369, 1372 aldehyde amidocarbonylation – rhodium-mediated hydrogenation of 720 – metal-catalyzed 1197 alkoxides (NaOtBu) 1612 aldehydes 1111 – as ligands 242 – decarbonylation of 526 alkoxycarbonylation 29, 123, 1563 – decarbonylative addition reactions 527 alkoxylation, palladium-catalyzed 456 – oxidative decarbonylative couplings 527 alkyl aldehydes 1326 aldimines 743 alkylaluminium 337 aldol adducts 1048 alkylaromatic compounds 479 aldolases 918 – homogeneous liquid phase oxidation 470 aldolization reaction 1101 alkylated amine 1380 Al(III)-salen complexes 282 N(3)-alkylated triazoles 1545 aliphatic aldehydes 729 alkylating agent 208 aliphatic amides 743 alkylation aliphatic amines/anilines, arylation of 752 – nitrogen heterocycles 1323

aliphatic carboxylic acid derivatives – TiCl4 with aluminium alkyl molecules 204 – decarbonylative elimination 529 alkyl hydroperoxides 543 aliphatic polycarbonates 280 alkylidene catalysts 1342 aliskiren 1091 1-alkylimidazoles 755 alkali formates alkylmetallocenium ions 208 – by acidolysis 1605 alkylpalladium complexes 159 alkali metal-catalyzed hydroamination alkylpalladium migration product 963 reactions 1413 alkylphenols 545 alkanes 1526 – oxidation 548 – borylation 1127, 1128 alkyl-substituted aromatic compounds 427 – carbon monoxide copolymerization 837 alkyl-substituted vinyl groups 507 – C-H bonds, selective oxidation of 1525 alkylvanadium halide 205 – coordination-insertion process 966 4-alkynals, cyclization of 1325 – hydroxylation 713 alkyne-dicobalt hexacarbonyl complexes – metathesis 1073 1291 – oligomerization 1076 alkynes – oxidation 705, 711, 714, 1526 – carbonylation 118–125 – selective oxidation of 1525 – complexes 1287 alkene isomerization, transition metal catalyzed – hydroamination catalyst 1380, 1391 – functionalized alkenes 1370 – hydroarylation of 1319 – metal-catalyzed isomerization 1365 – metathesis 1337 – non-functionalized alkenes 1367 – methoxycarbonylation reactions 120, 123 alkene metathesis 1071, 1337 – palladium catalyzed hydroformylation 58 – case study 1073 – photochemical carbonylation of 125 – catalysts optimization 1075 – reductive amination 729 – catalytic cycle 1073 – tetramerization 316 – Chauvin mechanism 1334 – trimerization 1211 alkenes alkynoates 142 – coordination-insertion process 979 alkynoic acid esters 118 – [2 + 2] cycloaddition of 1391 2-(2-alkynyl)anilines 1415 – enantioselective hydroamination of α-alkynyl indoles 1405 – three-component synthesis 1477 Index 1701

2-alkynyl substituted arenes amide functionality 1435 – cyclization 1206 amides allene insertion 1465 – large scale synthesis 1430 – allylation sequence 1465 – regioselective synthesis 1452 – carbonylative sequences 1468 amidinate catalyst 231 allenes amidinato ligands 194 – hydroalkoxylation of 853 amidocarbonylation – regioselective carbopalladation 1464 – metal-catalyzed 1197 allenynes – reaction 1198

– Mo(CO)6-mediated reaction 1302 amido(cyclopentadienyl)titanium allyl alcohol, to 4-hydroxy-butyraldehyde 54 compounds 198, 211 allylamines 1568 amination reactions 1583 – hydroformylation 56, 62 – efficient Buchwald biaryl phosphine allylation intermediate, cyclization 1465 ligands 438 π-allyl complex 1366, 1399 – efficient Josiphos-type ferrocenylphosphine allyl cyanide 61 ligands 442 allyl derivative 1106 – efficient trialkylphosphine and amino- allyl ether phosphine ligands 449–450 – arylation of 975 amine complex 1280 – Heck arylation of 974 – amine-N-oxide cycle 1514 – hydroformylation, regioselective 55 – hydroamination via oxidative addition allylic alcohols 627, 1056, 1511 of 1401 allylic aromatics – N-formylation 1428 – base catalyzed isomerization 1372 – nucleophilic attack 1398 allylic oxidation 706 – oxidative carbonylation of 150 N-allyl-4-methyl-N-(2-methylallyl) – phosphite, hetero-combinations 860 benzenesulfonamide 873 amine-containing cyclic diphosphine π-allylpalladium chloride 344 ligands 1164 2-allylphenol, oxidation 548 amine coupling 1447 alpha-olefins, metallacycles 312 amino acid dehydrogenase (AADH) 904 γ-alumina-supported silver clusters 1447 amino acid derivatives 1198 alumina surface 1070 amino acids (α-amino carboxylic acids) 752, aluminium alkyls 207 904 aluminium compounds 200, 205 – synthesis of 904 aluminoxane co-catalysts 208 D-amino acids 914, 915 Amgens’s hydroformylation approach 54 2-amino-1-alkanols 154 amidases 913 amino-alkenes – penicillin G amidase 913 – rare-earth metal catalyzed intramolecular amidation 1583 hydroamination of 1381 – alcohols 1444–1445 – thermodynamic profile, of intramolecular – aldehydes 1440–1442 hydroamination 767 – carboxylic acids 1429–1431 α-amino α-alkyl esters 1455 – esters 1437–1439 α-aminoalkyl radical 1121 – nitriles 1445–1449 amino-alkynes 1390 – oxime/oxime intermediates 1449–1452 – cyclization of 1382, 1398 amide bond formation 1445 β-amino-alkynes 58 – alcohol/nitrile coupling, ruthenium – hydroformylation 59 catalyzed 1444 amino-allenes 1385 – reactions 1428 β-amino and β-hydroxyl esters 680 amide compound 1278 aminocarbonylation 123, 1455–1456 amide formation – of alkynes 1455 – BEMP catalyzed 1439 – of aryl chlorides 1454 – palladium catalyzed 1441 – of heteroaryl bromide 1453 1702 Index

– metal catalyzed 1452 antimigraine drug 1201 – tert-butylamine as ammonia surrogate 1454 antipsychotics 1207 6-aminohex-1-yne 1408 aqueous-biphasic, homogeneously-catalyzed aminohydroxylation 1510 process 73 aminolysis 1271 aqueous hydrogen peroxide 546 – of esters 1438, 1439 aqueous-micellar solutions 869 aminomethylpyrrolidine 237 – with homogeneous and heterogeneous aminopentenes yields pyrrolidine catalysts 870 – cyclization of 1387 Arabidopsis thaliana 907 aminophosphine ligand 318, 450 Ar-Cl oxidative addition 957 (S)-1-aminopropan-2-ol 60 arenes aminotroponiminato calcium 1396 – alkanes, carbonylation of 1125 ammonium hexafluorophosphate 729 – C-H functionalization amorphous cobalt-phosphate (Co-Pi) 1141 –– borylation of 1315 amphiphilic phosphane-based micelles, –– palladium-catalyzed 1210 catalytic performance 856 – decarbonylative C–H arylation 528 analogous nickel complex 1176 L-arginine 904 Anderson–Schulz–Flory distribution 347 Ar–I oxidative addition, alternative anhydrides of dicarboxylic acids 912 pathways 960 anidulafungin 426 aromatic acids anilido complex 252, 1278 – industrial production of 482 aniline – metal-catalyzed decarboxylation 481 – accelerating effect 1269 – structures 472 – cobalt-catalyzed oxidative – synthesis, future developments 487 carbonylation 1278 – via liquid-phase homogeneous aerobic anion effect 962 oxidation 471 anionic alkali metal bases 1612 aromatic alcohols 1056 4-anisidine 728 aromatic amines anisoles – aromatic bidentate amines 258 – arenes, conversion in to 1634 – oxidative carbonylation 1262 – hydrogenolysis of 1634 – redox carbonylation 1262 anisyl derivative 1114 aromatic carboxylic acids annelated dihydrofurans, three-component – bifunctional activation 1272 synthesis 1465 – co-catalyst, role as 1268 annelated isoquinoline derivative, – manganese(II) oxide and sodium four-component synthesis 1466 hydroxide 470 annelated triazoline derivatives 1466 – protodecarboxylation of 533 – three-component synthesis 1467 aromatic C-H transformations 1315 – transformation into isoquinolines 1467 aromatic enone 1116 ansa-cyclopentadienyl-amido titanium aromatic hydrocarbons 207 complex 226 aromatic isocyanates ansa-lanthanocenes 1381 – large-scale generation 1261 anticancer cell sensitizing agent, imidazoline- aromatic polycarbonates based 1203 – synthesis of 274 anti-diastereomers 1511 – technological routes to 275 anti-Markovnikov addition product 736 aromatic triflates 415 anti-Markovnikov hydrocyanation 1368 aroyl-palladium bond 1200 anti-Markovnikov mechanism 503 Arthrobacter aurescens 917 anti-Markovnikov products 737, 1379, artificial metalloenzymes 849 1401 aryl alkyl carbinols anti-Markownikov regioisomer 1386 – Oppenauer oxidation 1628 anti-Markownikov regioselectivity 1395, aryl alkynes hydrogenation 58 1397 N-arylamides and acetanilides 1456 Index 1703 aryl amines asymmetric dihydroxylation (AD) 1510 – formation 436 – catalyst 709 arylarsenic 1486 – cinnamates and asymmetric alcoholysis (AA) arylating agents 415 of styrene 1511 α-arylation 757 asymmetric epoxidation 699 β-arylation 970 – of trans-2-heptene 705 N-arylation 752 – using of α,β-unsaturated ketones 700 aryl azides 729 asymmetric hydroamination catalysts 1387 aryl benzenesulfonates asymmetric hydrogenations 1051, 1086, 1087 – Pd-catalyzed amidation 441 – of imines 782 aryl boronic acids 1053, 1466 – of silyl enol ethers 783 aryl bromides 1121 asymmetric hydrosilylation 738 – hydroxylation of 458 asymmetric photocatalysis 1099 – Pd-catalyzed amination 436 asymmetric triaryl compounds 823 aryl chlorides 823 atactic material 200 – amination 439 atactic polynorbornenes 220 – Buchwald-Hartwig amination 448 atactic polypropylene 194, 217 – high turnover number Pd-catalyzed atactic polystyrene 242 amination 447 atazanivir 429 – hydroxylation of 458 atom transfer radical addition (ATRA) aryl diazonium salts 823 mechanism 897 aryl halides atom transfer radical polymerization – alkynylation of 754 (ATRP) 225, 882 – Buchwald-Hartwig amination 443 atorvastatin 916 – coupling with carbon nucleophiles 754 atropisomeric biaryl ligands 625 – decarboxylative trifluoromethylation 537 Au-NHC catalyst 1445 – oxidative addition 956 autothermal reforming (ATR) 40 – palladium-catalyzed alkoxylation 454, 456 avantium 1621 – palladium-catalyzed amination 445 azabutadiene formation 1479 – palladium-catalyzed coupling 449, 456, azametallocyclobutene 1390 953 aza-Michael addition 1551 – palladium-catalyzed hydroxylation 457 β-azido-ribose 1549 – Pd-catalyzed intramolecular azoxybenzene 1268, 1274 etherification 454 aryl iodides 752, 753 b – alkynylation of 755 Bacillus subtilis 912 – aminocarbonylation 1453 back-bonding interaction 958 – oxidative additions 960 backbone polymer chain 210 aryl ketones (R)-()-baclofen 1490 – decarboxylative synthesis 537 Badische Anilin- & Sodafabrik (BASF) 68 – transfer hydrogenation 632 – hydroformylation process 68 aryl mesylates – menthol process 1092 – Pd-catalyzed amination 448 Baeyer–Villiger monooxygenases aryloxy-function 192 (BVMO) 908 aryl–palladium bond 146 Baeyer-Villiger (BV) oxidation 908, 1054 γ-arylpropanoic esters 974 – of ketones 1485 α-arylpropionic acids 912 – one oxygen atom 909 aryl sulfonates 536 Baeyer-Villiger product 1500 aryl tosylates Barton decarboxylation reaction 533 – Buchwald-Hartwig amination 445 Bd/MeOH, telomerization of 368 – with Josiphos-type ligands 443 BDMS. see Bromodimethylsulfonium bromide – Pd-catalyzed amination 442 (BDMS) asymmetric BV oxidation 1488 Beckmann rearrangement 1451 1704 Index

benzaldehyde 474, 739 bidentate sp2-nitrogen ligands 168 benzamidinato ligands 194 BILN 2061 inhibitor 1346 benzeneboronic acid derivatives 1430 bimetallic catalysis 772 benzene carbonylation 1126 – Cu/Pd-catalysts 536 benzene derivatives 1100 bimetallic decarboxylative cross-coupling benzene oxidation 714 reaction 535 benzeneseleninic 1486 bimetallic phosphinimide complexes 230 benzhydrylamine hydroamination bimetallic Rh/Ni system 527 product 1393 (R,S)-BINAPHOS 59 benzimidazole 1323 (R)-BINAP/(R,R)-DPEN pair 657 benzofuranone 1470 BINOL-based ligand 854 benzofurans binol-complex 194 – palladium catalyzed synthesis 1206 – POOH derivative 643 benzoic acids 149 binuclear complexes 227 – decarboxylation 533 – chromium complexes 317 – halides 528 binuclear mechanism 317 benzolactam formation binuclear metallacycles 313 – via intramolecular aminocarbonylation 1455 biocatalysis 898, 902 benzonitrile 743 – choice of reaction systems 902 benzoquinone (BQ) 143, 504, 544 – cycle 900 benzothiophene 1570 – kinetic resolution/asymmetric synthesis 901 benzotriazole 1437 biodiesel 1593 benzoxazolones 151 – production 1636 N-benzoyl-L-glutamic acid 1536 bioinspired catalyst design 1572 N-benzoyl-L-proline 1536 – copper-based catalytic systems 758 benzyl alcohol 718 bioinspired diiron complexes 1659 benzyl benzoate, hydrogenation of 647 bio-inspired flavin mimics 1499 benzylic bromides biologically active quinones 543 – formation 481 biological screening 1085 – solvolysis 484 biomimetic ligands benzylideneacetone 730 – used in iron catalyzed alkane oxidation 710, benzylidene moiety 825 712 N-benzyl-N´-(2-arylethyl)piperazines 1413 – used in oxidation reactions 719 benzyne biomimetic oxidation, with perfluorinated – in-situ generation 1204 porphyrin complexes 719 berseran 1206 biotin binding pocket 850 BET surface area 1009 biotin moiety, diphosphine ligand 1572

BF2-bridges 1672 biotin–spacer–ligand scaffold 851 – cobaloximes 1674, 1677 biotin–streptavidin technology 850 biaryl diphosphines 634 Biox 168 bicyclic allylic amines 1415 biphenol/diamine 840 bicyclic compound 1109 BIPHEPHOS 36 bicyclic cyclobutane derivatives 1115 bipyridine bicyclic dienone 1300 – 2,2´-bipyridine 1143 bicyclic enones 1287 – 4,7-dimethylphenanthroline 1679 bicyclopentanoids – ligands 161, 1676 – palladium catalyzed synthesis 1204 bipyridyl pyrazolate 1142 bidentate carbene system 964 bisallenes 1466 bidentate diphosphines 357 bis-butadiene palladium complex 345 – ligands 161 biscationic iridium catalyst 1626 bidentate ligand, conformational flexibility 834 bis(η5-cyclopentadienyl) scaffold 191 bidentate phosphine–phosphoramidite bis(cyclopentadienyl)titanium(IV) ligand 1050 compounds 207 Index 1705 bis(diphenylphosphino)propane (dppp) 56, BP SaaBreTM process 117 1298, 1563 BP trimerization catalyst system 321 bis(fluorenyl)zirconocenes 210 Brichima process 546 bis(hydroxo) bridged dinuclear vanadium m,m´-bridged biaryldiphosphine 634 core 1532 Brintzinger-type ansa-metallocene bis-ligated MAO activated phenoxyimine 237 structure 192 bisoxazoline 169, 860 Brønsted acids 728, 729, 1397, 1516 bis(oxazolinyl)phenyl (phebox) ligands 738 – catalysis 1410 bisphenol A bromides, alkynylation of 755 – aromatic and aliphatic polycarbonate 2-bromo-4,6-dimethylaniline 749 structures 273 bromodimethylsulfonium bromide bis(phenolato) ligands 194 (BDMS) 1451 bis(phenoxy) catalysts 195 bromoindoles 1452 bis(phenoxy) complexes 194 bromomalonate 1116, 1119 bis(phenoxyimine) complexes 198 2-bromomesitylene bis(phosphine) palladium complex system 437 – hydroxylation recycling 458 bis(phosphinimino)methanide bis 1-bromo-2,6-naphthalenedicarboyxlic (dimethylsilylamide) complexes 1389 acid 487 bis(phosphinimino)methanide N-bromophthalimide (NBP) 866 cyclooctatetraene complexes 1389 N-bromosuccinimide (NBS) 866 bis(phosphino)amine ligand (PNP) 342 bubble-column reaction system 1041 1,2 bis-phosphinoethane scaffold 1093 Buchwald biaryl phosphine ligands 437 bispidine ligands 711 Buchwald–Hartwig aminations 412, 437, 824 black liquor 1630 Buchwald-Hartwig coupling 1478 bleaching catalysts building block aldehyde 28 – structures of ligands 523 bulky phosphines 359, 957 block copolymers 238 bulky phosphites N-Boc-2-aryl-4-alkynyl pyrroles – hydrolysis rates of 843 – three-component synthesis 1477 Burkholderia cepacia 912 N-Boc-4-iodo-2-substituted pyrroles butadiene 194, 248 – three-component synthesis 1476 – 1,3-butadiene 827, 1595 Boc-protected amino-esters 678 – diphosphines in telomerization 358 Bolm’s original catalytic system 1488 – hydroformylation 49 bonds – telomerization of 347, 350, 374, 849 – dissociation energies (BDEs) 811 butadiene polymerization – forming reaction 1203 – with aliphatic phosphine Co(II) complexes – between growing polymer chain (P) and and MAO 262, 265 transition metal 249 – by (anilidomethyl)pyridine Zr(IV) complexes

– strengths 1310 with Al(iBu2H)/MAO 253 borane 845 – with aromatic phosphine Co(II) complexes borate activation 232 and MAO 263 boric acid catalyst 1430 – by bis(phenoxyimino)TiCl2–MAO boron-based reagents 1434 catalysts 253 boron-capped tris(glyoximate) cobalt 1156 – by bis(phosphinophenyl)amido lanthanide boron trifluoride diethyl etherate complexes 271

(BF3
Et2O) 1448 – by Cr(II) bidentate phosphine complexes borosalicylic acid 121 with MAO 256 borylation 1316 – by (dibenzimidazolyl)Co(II)Cl2 complexes – of arenes 1319 and EASC 266 Boscalid 421 – by dichlorotitanium complex in combination bowl-shaped phosphine 360 with MAO 253 BP Cativa process 103 – by NCN–lanthanide complexes 271 BP chemicals process 334 – with (NNN)Cr(III) complex with MAO 257 1706 Index

– with (salen)Co(II) complexes and MAO 265 – hydrogenation 1604, 1607, 1610 butadiene telomerization 343, 353 – iridium pincer complex-catalyzed reduction – Smutny’s mechanism 345 of 895 n-butanal 75 – uses and storage 1601 n-butanol 1349 carbon nanofiber (CNF) 221, 222, 1044 1-butene 233, 337, 339 carbon nanotubes 221, 223, 1045 butene hydroformylation 46 carbon-nitrogen bond formation 2-butenes 1039, 1375 – palladium-catalyzed 436–450 (E)-2-butenyl acetate 357 carbon-oxygen bond formation η3-butenylpalladium complexes 357 – efficient ligands, development of 455 tert-butyl amine – palladium-catalyzed 450–458 – anti-Markownikov addition 1392 carbon-sulfur bonds by catalysis, formation n-butyl cinnamate synthesis 1029 of 1570 t-butyl hydroperoxide 504 carbonylation 92, 115, 1041, 1196, 1297, 1300, tert-butyl substituents 1162 1311 2-butynes 722 – flavones and quinolines synthesis 1199 n-butyraldehyde 45, 91 – rhodium-catalyzed 1274 BV monooxygenases (BVMOs) 1497, 1499 carbonylative cyclization BV oxidation 1492, 1499, 1500 – palladium-catalyzed 1199 – of cyclic ketones 1487 carbonylative triazole synthesis 1202 – diphosphine PtII complexes 1492 carbonyl complex 1271 – of ketones 1486, 1493 carbopalladation processes 1468 4-carboxybenzaldehyde (4-CBA) 483 c carboxylate-directed hydroxylation 1528 caesium carbonate 759 – followed by lactonization catalyzed by Fe California red scale 1110 (bpbp) 1527 1,3-calix-diphosphite ligand 855 carboxylate-ligated Ru similar 887 Candida antarctica 912 carboxylates, ligand-free aminohydroxylation Candida cylindracea 912 of 1510 Candida rugosa 912 carboxylic acids 1486, 1530 caprolactam 1451 – amidation 1427–1433 – fermentation of 1617 – amidation catalyst – nylon-6, monomer for 1625 –– boric and boronic acid 1430 carbamates – amine 1427 – rhodium-catalyzed transfer 1570 – conversion 477 – synthesis, selenium catalyst, use of 1279 – decarbonylative cross-coupling carbamoyl complex 1271, 1278 reactions 531 carbamoyl compound 1280 – decarbonylative elimination 528, 529 carbazoquinocin C 1103 – decarbonylative Heck reaction 530, carbene-oxazoline 640 531 carbenes 1310 – decarboxylative homo-and cross- – Ru complexes 640 ketonization 534 carbocations 1447 – promotor effect 1267 carbo/heterocycles cis-carboxypalladation 507 – steric and electronic variations 837 carboxypeptidase A 1572 carbohydrate-based CaRLa 1611, 1612 benzenesulfonamides 1549 Carroll rearrangement 537, 538 carbomethoxy cycle 131 cascade molecular queuing processes 1467 carbon allotropes 1100 cataCXium ligand 837 carbon catalyst 117 catalysis carbon dioxide 280, 1601 – challenges 1380 – catalytic hydrogenation of 832 – without metals 643–644 – emissions 1601 catalyst 240, 999 Index 1707

– based on half-titanocene 252 – alkylzirconocene complexes 1394 – based on iron-terpyridine complexes 258 – amphiphilic molecules 1497 2+ – based on late transition metals 196 – cobalt complex [Co(bpy)3] 1676 – for coordinative polymerization of – cobalt polypyridine complexes 1167 styrene 201 – late transition metal ethylene polymerization – deactivation 1268 catalysts 240 –– CO complexes, role of 1620 – Ni(II) diimine 240 – efficiency 1489 – palladium species 956 – heterogeneous 999 – phenyl complex 956

– high-throughputscreening 198 – [Rh(COD)L2*] complex 1562 – homogeneous 1000 cationic Ni(II) catalysts – leaching 117 – mechanism of branch formation 241 – recycling 821 Cativa process 95, 103, 104 – residues 337 cavity-containing tetrahedral metal– – selectivity 1001 ligand 852 – stability 161 C-B bond 1328 ––substrate complex 1537 C-C bond rotation 974 catalytic C–C-coupling reactions 28, 413, 745, 1015 – active complex 962 – calculated molecular structures of key – active species 1099 intermediates 967 –– binuclear model 320 – proposed pathways 967 – activity 1009, 1026, 1053 CˆC double bonds 651 – aldoxime rearrangement 1449 CˆC hydrogenation 622

– Beckmann rearrangements 1451 1-C6/1-C8 α-olefin 311 – click reactions 1550 CC π system 1412 –– copper-catalyzed azide-alkyne CECE mechanism 1150 cycloaddition (CuAAC) 1542 Ce(IV)-periodato complexes 1517 –– quantitative chemical cellulases 1617, 1618 transformations 1541 cellulose 1581 –– ruthenium-catalyzed azide-alkyne – oxidation to CO 1618 cycloaddition (RuAAC) 1548 cerium(IV) salts 1517 – copolymerization cetalox 664 ––of ethylene- or propylene-oxide with carbon cetyl pyridinium bromide (CPB) 855 dioxide 226 cetyltrimethylammonium – decarbonylative/decarboxylative hydrogensulfate 854

processes 524 C18-fatty acids 1582 – hydroamination 1402 CH activation 435 – hydrogenation 723 – with organometal compounds, –– of ketones 724 photochemically supported 1124 –– of nitro-aromatics 729 chain-shuttling 199 –– by P/B Lewis Pairs 775 – agent 224 –– without additional Lewis base 777 – polymerization 238

– intermediate Co2(CO)6 1288 chain walking mechanism 196 – oxidation of N-benzoyl-L-proline 1536 Chan–Evans–Lam-type process 543 – performance 1073 Chauvin mechanism 1335 – polymerizations 247 Cβ-H bond 967 –– of olefins 203 C-H bond 1307 catalytic tetramerization systems 322 – activation 1209 catalytic trimerization systems 318 – aminocarbonylations 1458 catechol (CA) 546 CH2CH2 bridge 215 cation exchanged zeolites 1408 chelate ring strain effects 371 cationic chelating – alkene polymerization 1071 – assistance strategy 1308 1708 Index

– assisted functionalization of arenes 1319 – acemic mixture of, 214 – bisphosphine dissociation 957 chiraphos ligand 323, 1092 – ligand 162 chlorination 1583 – phosphinimide 230 chlorine-coordinated catalysts 243 C–H elimination 313, 1398 chloroalkylaluminium 336 chemogenetic optimization 850 α-chloroamide chemoselectivity 119, 370, 1515 – palladium-catalyzed carbonylation 1202 chenphos 635 chlorobenzene 1612 C–heteroatom 745 chloro(1,5-cyclooctadiene)rhodium(I) C–H functionalization 525, 1210 dimer 529 – oxidative decarboxylative couplings 540 2-chloroethanol 502 C-H hydroxylation studies 709 chloroformates 1469

CH3I oxidative addition 1561 4-chloroquinaldine chiral β-amino acids 633 – catalyst recycling amination with chiral amino-alcohol titanium complexes 1396 morpholine 450 chiral 2-aryl propionic acids (profens) 60 chlorosulfonic acid 1434 chiral backbone moiety 1495 C-H oxidations 1528 chiral bicyclic enones 1292 – regioselectivity 1535 chiral bis(diphenylphosphino-1,2- chromacyclopropanone structure 1102 dimethylethane) (DPPDME) ligand chromium catalysts 255, 1531 frameworks 323 chromium–chromium interaction 317, 318 chiral bisoxazoline ligand 727 chromium ethylidene complex 326 chiral boranes 780 chromium heteroscorpionate complexes 324 chiral building blocks 1089 chromium tris(acetylacetonate) 325 chiral centers 1089 chromium tris(2-ethylhexanoate) 320, 325 chiral (S,S)-1,2-diphenyl-ethylenediamine cinacalcet 429, 431 (DPEN) ligand 658 – hydrochloride 415 chiral enamine 1103 – synthesis 53 chiral hydrogenation catalysts 1047 cinchona alkaloid ligands 1510 chiral hydroxynitrile, synthesis of 918 cinnamaldehyde chiral iodine derivative 1123 – selective formation 974 chiral iron complexes, for asymmetric citronellal 1087 epoxidation of olefins 698 Clariant’s process 148 chiral ligand, used in oxidative kinetic CLAs. see conjugated linoleic acids (CLAs) resolution 717 cleavage of lignin chiral lithium bisoxazoline (BOX) – oxidative approaches 1634–1636 catalyst 1414 click reactions 1215 chiral metal complexes – catalytic, non-catalytic, and triggered 1552 – generic structural elements 623 C-N bond-forming reaction 759, 1384 chiral metallocyclophanes, rigid square- C=N groups shaped 854 – hydrogenation 633 ´ chiral N,N -dioxide/Sc(OTf)3 catalyst 1496 – state-of-the-art 632 chiral phosphine complex 1297 13C NMR spectroscopy 205 chiral phosphinopyridine ligand 1490 CNT filled PP, advantage 223 chiral phosphorus ligands 829 cobaloxime 1672, 1674, 1682 chiral pool-based intermediates 1090 cobalt 113 chiral pyridine 1098 – based catalytic system 1646

chiral supramolecular triangle 853 cobalt-based H2-evolving catalysts 1667 chiral systems 193 cobalt bis(dithiolene) catalysts 1178 α-chiral thioethers 1571 cobalt bis(iminopyridine) complex 1167 chiral titanocene 213 cobalt catalysts 260, 1099, 1159, 1183 chiral tridentate bisoxazoline ligands 738 – electrocatalytic water oxidation 1142 chiral zirconocene compounds – with Mn/Br 478 Index 1709

– MOS 1184 computational chemistry 1080 – structures 1672 computed free energy profile 963 cobalt-catalyzed methanol carbonylation 96, conductive metal oxides 1137 97 cone angles 229, 836 cobalt complexes 1677 (E)-configured olefins 527 – with 2,6-bis(imidate)pyridyl ligands 268 conformational flexibility 834

– H2 production 1157 coniferyl alcohol 1630 – ligated by imino- or amino-pyridyl alcohol conjugate addition reaction 1640 ligands 267 conjugated dienes, stereospecific – mediated radical reactions 1108 polymerization of 249 cobalt dichloride complexes 266, 268 conjugated linoleic acids (CLAs) cobalt glyoximates 1151 – isomerization to 1373, 1642 cobalt hangman porphyrin complex 1173 constrained geometry 191 cobalt hydride species 1279 – catalysts 191, 226, 227, 230 cobalt(II) glyoximate complexes 1155 continuously stirred flow reactor (CFSR) 74 cobalt(III) hydride 1675 continuously stirred tank reactor (CSTR) 483 cobalt porphyrin catalysts 1172 conversion of HMF into caprolactam cobalt-Schiff-base complex 1274 – lactonization of 1,6-hexanediol, importance

CO2-based building block 1608 of 1625 Co-based catalysts 30 co-oligomerization 1584 C-O bond coupling – of linoleic methyl ester with ethylene 1586 – palladium-catalyzed alkoxylation 447 cooperative catalysis 643 2+ [Co(bpy)3] 1675, 1676, 1677 cooperative iron-catalyzed hydrogenation of Co-catalyzed hydroformylation imines 728 – bicyclic phosphines 34 η2-coordinated acrylic acid complex 1611 Co-catalyzed reaction κ2 coordination mode, P-S ligands 1560 – additives 1288 coordinative chain transfer polymerization – catalyst precursors 1291 (CCTP) 769 – enantioselective reaction 1292 co-oxidation processes 467

Co2(CO)8 1290 copolymerization 156, 191–199, 211, 212, 220, coconut oil 227, 233 – hydrogenation 1644 – of 5-alkylnorbornenes 246 CO-diiron complex 1659 – of butadiene and isoprene 257 codimerization 334 – of CO2 and epoxide to polymeric [Co(dmgH)2PyCl] 1677, 1681 carbonates 281 CO2/epoxide copolymerization 281, 282, 284 – of ethylene 199 Co-ethyl-hexanoate 30 – of norbornene (N) and ethylene by different Co(III)-hydroxo complexes 1279 metallocene/MAO catalysts 220, 246 Co(III)salen catalyst system 282 – properties 192 Co(II)salen complex 1497 copolymers 192, 224, 244 CO insertion in radical reactions copper catalysis, new future in 761 – palladium catalyzed 1123 copper-catalyzed arylation 744, 746, 748, 758 Co(IV)Co(IV) peroxo species – of amides and heterocycles 753 – hydrolysis of 1143 – of amines 752 CO ligand 728 – of phenol 759 combined cyclization–hydrosilylation – of pyridazinone 760 reaction 766 copper-catalyzed α-arylation of ketones 758 CO migratory insertion 1198 copper-catalyzed C-C bond formation 754, commercially valuable syndiotactic 763 1,2-polybutadiene 261 copper-catalyzed C-N bond-forming co-monomer market 309 reaction 750, 753, 763 Co-monosubstituted Keggin POMs 516 – in GlaxoSmithKline’s synthesis 760 composite materials 222 – in scalable synthesis 761 1710 Index

– in synthesis of API 762 – PEPPSI-NHC complex 823 copper-catalyzed C-O bond formation – products, cyclization 1208 reactions 746 – yielding 818 – for synthesis of phenols and aryl ethers 746 cross-dehydrogenative coupling 1441 copper-catalyzed cross-coupling with cross-linked polyvinylpyridine 117 malonates 755 cross metathesis (CM) 873, 1348 copper-catalyzed cyanation reactions of aryl crotyl halide 245 halides Cr-pyrrolyl ethylene trimerization catalyst – developed by Buchwald, Taillefer, and system 321 Beller 755 crude boronic acid 421 copper-catalyzed direct arylation of cryoscopic measurements in benzene 208 ammonia 751 crystalline polyethylene 240 copper-catalyzed enantioselective α-arylation crystallization rates 222 – of activated methylene derivatives by Ma crystallization temperature 222 757 C-S bond formation 1570, 1571

copper-catalyzed Hurtley-type reactions 756 C2-symmetrical octahedral complexes 196 copper-catalyzed Sonogashira-type C2 symmetric cis-X/cis-N/trans-O reactions 756 geometry 236

copper(I) chloride 759 C2-symmetric metallocenes 215 copper(II) ions 1538 CuAAC reactions 1542, 1543 copper in scalable synthetic processes 758 – of benzyl azide 1545 corticotropin releasing factor (CRF) 759 – transition state-based scheme 1543 Corynebacterium glutamicum 904 Cu-catalyzed electrophilic fluorination Co(salen) complexes, in micellar media reactions 851

– oxidation of substituted CuCl2 acetaldehyde 502 cyclobutanones 1498 Cu halides 143

Cossee–Arlman mechanism 315 Cu4I4(H2O)4 catalyst 1446 CO2 switchable soluble catalysts Cu(II)-mediated oxidative Glaser – in Rh-catalyzed hydroformylation 883 couplings 1547 coumaryl alcohol 1630 Cu(II)-oxazoline catalyst 1489 counterion 107 Cu(II)-oxazoline complex 1488 coupling reaction 414, 1004, 1052 Cu nanoparticles 1079 – of alcohols with amines 1445 Cu/NHC complex 748

– of benzylic alcohols with amines 1444 Cu(OAc)2 1432, 1487 – carboxylic acids 1430 Curtin-Hammett situation 975 – between furfural and secondary alcohol 1623 Curtius rearrangement 1471

– Pd(PR3)2-catalyzed 964 Cu/ZnO/Al2O3 catalysts 1557 covalent anchoring 1056 C-X coupling chemistry 1094 covalent bonding 1002 cyanating agent 755 C–P bonds, via umpolung 842 cyanation of aryl halides 754 [Rh(S-tBu)(CO)] complex 1563 cyanide synthons 1445 Cr-based homogeneous catalyst system 311 cyclic alkanes 1526 Cr-Cr multiple bond 318 – dehydrogenation 894 Cr(III) complexes 257, 282 cyclic amide formation critical micelle concentration 855, 865 – iron catalyzed C-C bond cleavage 1457 crixivan 1195 cyclic anhydrides crizotinib 426 – decarbonylative additions 530 cross- and self-metathesis of methyl cyclic benzyl hydrocarbons 1456 oleate 1589 cyclic enamine 1385 cross-coupling 745, 751, 953 cyclic N-alkyl imines 640 – disadvantage 412 cyclic olefins 220, 244 – multicomponent 1203 cyclic ruthenate 1520 – palladium-catalyzed 953, 1203 cyclic urea 1432 Index 1711 cyclic voltammogram (CV) 1137 cycloolefin homo- and copolymers 218, 220 cyclizations 1100 cyclopentadienyl-cobalt moiety 1559 – of amino-dialkene 1384 cyclopentadienyl-free rare-earth – multicomponent cross-coupling catalysts 1389 reactions 1205 cyclopentadienyl (Cp) ligand 218, 229, 1162 [2 + 2] cycloaddition cyclopentadienyl-NHC complex 740 – steric constraints 1393 cyclopentane derivative 1108 [2 + 2 + 1] cycloaddition 1287, 1300 cyclopentanol 730 [3+2]-cycloaddition-hydrolysis 1520 cyclopentanones cycloaddition reaction 1101, 1517 – BV oxidation of 1493 – metal-based 1212 – derivatives 1102 [2+3] cycloadditions 1465 cyclopentene 218, 220 cycloalkanes 1313, 1526 – polymerization 220 cycloalkanones cyclopropenium ion 1451 – asymmetric oxidation of 1499 cyclopropylidenes cyclobutane derivative 1114 – cycloaddition 1213 meso cyclobutanones 1498 CycloteneTM 420 cyclobutanone derivative 1103 cytochrome P450 716 cis-substituted cyclobutyl-benzothiazole cytotoxic epothilones 1345 pyridazinone 761 cyclocarbonylation 1455 d – iron mediated 1102 Dakin reaction 1500 cyclodextrins (CDs) 847, 1148, 1537, 1538 DAPTA (3,7-diacetyl-1,3,7-triaza-5- 1,4-cyclohexadiene 497 phosphabicyclo[3.3.1]nonane) 1664 cyclohexa-2,5-dienes 1415 Davy process technology (DPT) 47 cyclohexane 708, 710, 1532 dealcoholysis 237 – oxidation 468, 510, 711 de-aromatized ruthenium (PNN) pincer – radical-chain oxidation of 518 complex 1443 cyclohexanol 511, 1056, 1532 decarbonylations 1300 cyclohexanone monooxygenases – addition reactions 529 (CHMOs) 1497 – carbosilylation reactions 533 cyclohexanones 726 – carbostannylation 529 – desymmetrization and kinetic resolution – cross-couplings 532 of 1496 – Heck reactions 530 – formation, during cyclohexane – Negishi reaction 532 autoxidation 511 – transition metal-catalyzed 529 meso cyclohexanones decarboxylation 524, 532, 1431, 1530 – enantioselective oxidation 1494 – 1,2-addition 539 cyclohexene 722 – addition reactions 539 – disproportionation 1019 – allylation reaction 537, 538 cyclohex-2-enone 724 – carboxylic acids 532 cyclohexenones – coupling 535 – derivative 1102 – cross-coupling 535 cyclohexylacetaldehyde 1119 – cross-ketonization 534 cyclohexylacrylate 1052 – Heck reaction 540 cyclohexylamine 1292 – ketonizations 534 cyclohexyl(diphenyl)phosphine 1006 – Sonogashira reactions 537 cyclohexyl hydroperoxide 510, 706 – trifluoromethylations 537 – dehydration of 516 1-decene 246 cyclohexyloxy radical 512 – hydroformylation of 47 cyclometalated platinum(II) acetylide – Rh-catalyzed hydroformylation 856 PSs 1668 degenerative group-transfer coordination 1,5-cyclooctadiene 49 polymerization 199 1712 Index

dehydration reaction 477 N,N-dicyclohexylimidazolyl carbene dehydroamino acid 638 moieties 1545 dehydrogenases dicyclopentadiene 205, 225 – alcohols synthesis 903 – hydroformylation of endo/exo-mixture 50 dehydrogenation 1300 Diels–Alder reaction 170, 525, 867, 1550 dehydrogenative amide formation diene polymerization mechanism 249 – Milstein’s Ru-PNN catalyzed 1443 diene polymerization precatalysts 771 dehydrogenative coupling, rhodium- 1,3-dienes, oligomerization of 826 catalyzed 1620 dienes, unconjugated 1374 dehydrogenative cross-couplings 542 diester, acid-catalyzed hydrolysis 1628 dehydroxylation 1070, 1509 diethers (2,2-diethyl-1,3- density functional theory (DFT) 315, 954 dimethoxypropane) 204 – calculations 137, 733 diethylamine 1413 – computational approach 973 diethylene glycol dimethyl ether 646 – modeling studies 891 diffusion coefficient 1008, 1009 deprotonation 813 diffusion rates 1001 designer surfactant 866 diffusion–reaction model 1014 desired Rh-catalyst, P/Rh ratio 33 diflunisal 427 desulfurization 815 2,5-diformylfuran (DFF) 1624 desymmetrization 1,2-difuctionalized building blocks 1509 – and kinetic resolution of cyclic ketones diglyoximate cobalt complexes 1151, 1155 1495 5-endo-dig reaction 1382

– of meso cyclohexanones 1494 dihalide complexes [(diimine)NiBr2] 240 detoxification trans-dihydride ruthenium complex [RuH2 – of xenobiotic compounds 906 – (tBu-PNN)(CO)] 653 deuterium isotope effect dihydrido-rhodium complex 1402 – advantage 1620 dihydroisobenzofuran derivatives deuterium labeling 313 – three-component synthesis 1474 DFF. see 2,5-diformylfuran (DFF) dihydroquinazolines 1323 + D2/H exchange 1568 dihydroxyacetone phosphate (DHAP) 918 diafenthiuron 758 – by acid hydrolysis 919 dialkyl carbonates 154 – dependent aldolases 919 dialkyl complex 196 – dependent enzymes 919 1,3-dialkylimidazolium chloride 334 – phosphorylated ketone 919 dialkylphosphinobiphenyl ligand 439 dihydroxybenzenes 546 dialkyl phosphites 1,1´-dihydroxyketones 1517 – hydrolysis of 843 dihydroxylation 701, 705, 1509, 1516, 1521, diamido-ligands 193 1590 diaminocyclohexane – olefins and related reactions 1509 – backbone ((S,S,R)-mcpp) 1528 cis-1,2-dimethylcyclohexane 708 1,2-diamino-cyclohexane (DACH) 656 cis-dimethyl-cyclohexanol 711

dianionic N2O2-ligand systems 1274 diimine ligand 968, 1157 dianion mechanism 109 diiron complexes diaryl ethers – host–guest supramolecule 1148 – nickel catalyzed reductive cleavage 1633 – immobilization 3-(diarylmethylene)indolin-2-ones 1473 –– GC and gold electrodes 1179 – three-component synthesis 1473 – three-component system 1664 N,N´-diaryl-ureas 152 1,4-diisopropylbenzene 470 diastereoface selectivity 217 β-diketiminato ligands 1390, 1396 diastereotopic sites 217 diketone product 1531 diastereotopic transition states 213 1,2-diketones 1517 dicarbonylation 122 dimanganese complexes 1148 dicobalt hexacarbonyl complex 1287 dimerization 328 Index 1713

– of butadiene 344 – in n-regioselective Rh-catalyzed – of propene 329 hydroformylation 38 – with water 346 diphosphinoethane 978 DimersolTM process 332, 334, 335 diphosphites 843 dimetallocyclodecene 317 – synthesis 841 2,6-dimethoxybenzoquinone 544 dipicolinato Mo(VI) peroxo complexes 1486 3,4-dimethoxybenzyl alcohol 720 dipolar cycloaddition reactions 1215 dimethoxycarbonylation 118 1,3-dipole formation 1215 1,2-dimethoxyethane (DME) 325 2,2´-dipyridylamine ligand 324 2,2-dimethoxypropane (DMOP) 1263 di(pyrrolyl) amine 1392 2,4-dimethybenzaldehyde 485, 486 direct amide bond formation 1428 N,N-dimethylacetamide (DMA) 504, 505 direct dehydrogenative coupling of amines 1444 2,6-dimethylaniline 1391 discodermolide 1090 1,4-dimethylbenzene (p-xylene) 470 dissociative monophosphine pathway 959 2,3-dimethylbutenes (DMBs) 330, 333, 1,2-di-substituted alkene 1382 334 1,1-disubstituted olefins 1513 dimethyl carbonate (DMC) 156 cis-2,5-di-substituted pyrrolidine – from cyclic carbonates 280 products 1414 – by means of oxidative carbonylation of 2,3-disubstituted quinoxalines 644 methanol using 280 2,6-di-tert-butylphenol (DTBP) 547 – synthesis 279 dithiolato brigdging ligands 1562 dimethylchlorosilane 1592 dithiolene ligand, redox-active 1177 2,6-dimethylcyclohexanone 1494 divanadium-substituted γ-Keggin 1,2-dimethylcyclopentadienyl ligands 217 polyoxotungstate 549 N,N´-dimethylethylenediamine 754 divinylarenes intermolecular dimethylformamide 1608, 1609 hydroamination 1386

N,N-dimethylglycine hydrochloride 759, 760 dmgH2 (dimethylglyoxime) ligand 1668 2,4-dimethylhexanoic acid 1528 DMP. see 2,4-dimethyl-3-pentanol (DMP) dimethyl itaconate 722 DNBSA. see 2,4-dinitrobenzenesulfonic acid 4,4-dimethyl-2-oxazoline, alkylation of 1323 (DNBSA) 2,4-dimethyl-3-pentanol (DMP) 1637 1-dodecene, hydroformylation 855, 875 N,N-dimethyl-p-nitrobenzamide 743 dodecylbenzenesulfonate (DBS) 855 2,5-dimethylpyrrole 340 domino processes 1464 dimethylsilylene bridge 215 σ-donating alkoxy group 970 dimethyl terephthalate 26 donor-substituted proline 532 N,N´-dimethylurea 1429 double bond metathesis 1640 dinitroarenes 1267 double bond opening polymerization 218 2,4-dinitrobenzenesulfonic acid double cross-coupling (DNBSA) 1449 – benzofuran derivative (NuY=YO) 1206 dinitrogen catalyzed reduction 898 Douglas-fir beetle 1110 dinuclear dithiolato-rhodium complex 1562 Dow Chemical 349, 361 dioxirane mediated oxidations 1527 Dow Chirotech 631 dioxyloreol 664 downstream processing 105 dipalladium diphosphine complex 966 DuPont adiponitrile process 1367 diphenols 544 dyad structure 1665, 1666, 1683 diphenoquinone (DPQ) 544 dynamic kinetic resolution (DKR) 902 diphenylacetylene 722 diphenyl carbonate (DPC) e – selectivities 278 earth-abundant metal 1655, 1667 – synthesis 277 Eastman acetic anhydride process 107, 109 1,2-diphenyl-ethylendiamine (DPEN) 656 egg-yolk catalysts 1001 diphosphine ligands 120, 1034, 1561 elasticity 207 diphosphines elastomeric polypropylene 194 1714 Index

electrocatalytic H2 production 1152, 1160, enol ether 1106 1163, 1168 enyne metathesis 1335 electro-chemical-electro-chemical (ECEC) – mechanism 1335 mechanism 1177 enzymatic reactions 902 electrochemical proton reduction 1181 enzymatic reduction 903 electrochemical water oxidation 1135 Enzyme Commission (EC) 899

– O2 catalyzed by organometallic enzyme deactivation 900 compounds 1136, 1142–1146 Eosin Y 1674 electrochemical water reduction epoxidation 1073, 1123, 1590

– H2 catalyzed by organometallic – of cyclooctene catalyzed by Fe(BPMEN) and compounds 1146 –1187 Fe(TPA) complexes 695 electron-deficient α,β-unsaturated ketones 539 – of cyclooctene with iron catalysts and

electron density 1331 H2O2 704 electron donating character 1318 – of olefins 694, 702 electron-donating groups 835, 959, 1668 epoxides 281, 1019, 1521, 1590 electronic effects 106, 1316 epoxyalkyl 171 electronic excitation 1097 EPR spectroscopy 243 electron ligands 197 erucic acid 1582 electron transfer mediators 1514 Escherichia coli 850, 909 electrophilic aromatic substitution 1316 esterases 910 electrophilic cationic palladium esters 1048, 1583 complexes 245 – hydrogenation of 645 electrophilic metal centers 1308 – double bond modifications 1639 electrophilic radical 1121 ethene electropolymerization 1141 – Cr-pyrrole catalyzed trimerization 348 electrostatic component (Δq) 971 etherification 1583, 1593 eletriptan 415 ethoxylates 1583 β-elimination 1311, 1335 ethylbenzene 467 – mechanism 308, 312 ethyl benzoate 204 enamides 635 ethylene 194, 203, 205–207, 209, 233, 243, 768, β-enamine amide 1349 – hydrogenation of 633 – π*-acceptor character 964 enamines 1380 – alternating copolymerization of 159

enantioenriched lactic acid 61 – with aqueous PdCl2 solutions 499 enantiomer 175 – bridged complex 227 – molecules 1089 – dimerization of 336 enantiopure – π-donor character 964 – acyloins 1521 – methacrolein via hydroformylation 44 – aminoalcohol 1511 – non-alternating copolymerization of 162 – nitrile 1098 – radical copolymerization of 158 enantiopurity 167, 1510 – trimerization 339, 340

enantioselective 732, 1047, 1048, 1338 ethylenediamine (RuCl2(P2N2) 666 – BV oxidations 1491 ethylene glycol 957, 1004, 1014 – FLP-catalysis 779 ethylene-graft ethylene/propene copolymers, – hydroformylations 1093 reaction scheme for 212 – hydrogenation 622, 1092 ethylene/1-octene copolymerization 233 – metal-free hydrogenation using molecular ethylene polymerization 207, 230, 231, 235, hydrogen 779 243, 315, 325 – synthesis 1338 – catalysts 230, 235 encapsulated cobalt(III) complexes 1674 ethylene/propene copolymer 211 energy-efficient manner 1135 ethylene propene diene monomer (EPDM) enoate reductase (ER) 905 210, 232, 1369 enol aldehyde 1101 ethylene/propene macromers 211 Index 1715 ethylene–styrene copolymers 228 fexofenadine 55 ethylene–styrene interpolymers 228 fibers 222 2-ethylhexanol (2-EH) 45 FI catalysts 233 ethylidene diacetate (EDA) 110 first-order dependence 106, 109 ethylidene norbornene 205, 1369 Fischer indole synthesis 1201 ethyl isonicotinate 651 Fischer–Tropsch synthesis 48, 328, 693, 1013, ethyl 3-methylbut-2-enoate 722 1350, 1615 2-ethynylaniline derivatives 1407 Fischer type carbene 1103 1-ethynylcyclohexene 731 flash-dihydroxylation 1516 European Congress of Chemical Engineering flavin 1514 (ECCE) 1150 – derivatives 1500 exogenous thiolates 1568 flavinium salt 1500 exothermal reaction flavones 1478 – heat release 319 – three-component synthesis 1478 exothermic salt formation 1604 flow chemistry 1094 experimental diimine complexes 968 fluid catalytic cracker (FCC) 1375 Exxon/Mobil process 68, 69 fluidized powder bed reactor (E/Z) vinyl N-heterocycles 1385 – for syndiotactic polystyrene production 244 fluorenyl-catalyst 192 f fluorescein complex 1682 FAME. see fatty acid methyl ester (FAME) fluorination 235, 1538 Faradaic efficiency 1138, 1144, 1155, 1170, formamide 1436, 1608, 1610 1177 – synthesis of 1609 Faradaic yields 1149, 1182, 1184 formamide, transamidation of fats 1581 – (diacetoxyiodo)benzene (DIB) molecule 1582 catalyzed 1436 – transesterification with methanol 1583 formamidine formation 813 fatty acids 1583 formate dehydrogenase (FDH) 905 – based monomers 1636 – cofactor recycling system 922 – derivatives 1646 formic acid 97, 1603 – processing of 1583 formic acid trihexylamine (NHex3) salts 1607 fatty acid methyl ester (FAME) 1583, 1638 formylation of amines – enantioselective epoxidation 1645 – iridium catalyzed 1440 fat valorization 1637 – zinc catalyzed 1428 Fe-catalyzed olefin oxidations 1521 formylation reaction 1428 Fe complexes 642 fossil fuels 1655, 1656 feedstock free radical chain mechanism (FRCM) 475 – oils obtained 1637 free radical coupling 481 freeze-drying 1047 [FeFe]-H2ase 1558, 1559, 1658, 1661, 1663, 1665 Friedel–Crafts alkylation 851 – active site 1150 – of aromatic amine 1395 – structure of active site (H-cluster) 1658 – of indoles 851 – NiFe-hydrogenases 1147 Friedel–Crafts reaction 350 – organometallic compounds 1658 Fru-aldolases (FruA) 919 Fe(III) complexes 713, 1521 frustrated Lewis pair (FLP) 644, 774 Fe-Mo-S nanoclusters 1558 – catalyzed hydrogenations 775 Fe-Ni-S catalyst 1558 – catalyzed hydrosilylations 778 fermentable sugars (bioethanol) 1632 – in catalysis 775 ferrocene based ligands 625, 635 – in hydrogen activation 774 ferrocenyl 1092 fuel cell applications Fe-S enzymes 1559 – using NiMo-catalysts 1558 Fe(V)-oxo species 712 functionalized amide bond 1431 1716 Index

functionalized olefins Grignard reagents 426, 427, 429, 816, 818, 896 – copolymerization of 169 Grubbs catalyst 1641 – hydroformylation of 50 Grubbs–Hoveyda Ru complexes 881, 1053 – hydrogenation of 637 functionalized tetrahydroisoquinolines h – three-component synthesis 1470, 1471 Haber–Bosch process 693, 897 furfural 1622 Haber–Weiss radical chain mechanism 706 – benzoin condensation 1623 Halcon and Eastman Chemical Company 106 – hydrosilylation 1622 half-sandwich catalysts 191, 192 – reactions of 1622 halide-substituted dithiolene cobalt furfuryl alcohol catalysts 1176 – acid-catalyzed rearrangement 1622 haloacrylates 142 fused-ring cyclocarbonylation reactions 1200 ortho-haloarene carbonylation reactions 1200 halocarbons 205 g halogenated alkynes 1546

Ga4L6 anionic tetrahedral capsule 852 4-halo-pyrazoles gas–liquid interphase 1003, 1008 – four-component synthesis 1475 gas–liquid partition coefficient 1004 Halpern-type selectivity 970 gasoline additives 335 Hammett relationship 479 gas-phase hydroformylation 1023, 1035 Hantzsch ester 1117 gas-phase hydrogenation 1048 Hantzsch reaction 1195 gas recycle 31 H-bonding thiourea catalyst 885 gel-permeation chromatography (GPC) 233 head-to-head coupling 827 gem-dialkyl activated amino-alkenes 1389 heat management 1013 Gibbs free energy (ΔG) 957 heat shock protein 90 (Hsp90) inhibitor 760 Glaser reaction 431 heat transfer 244 glass autoclaves 1087 Heck arylation 414 glass transition temperature 221, 245, 246 Heck catalytic cycle glassy carbon (GC) 1139 – Pd(II/IV) redox pair 978 glucose Heck cross-coupling reaction 416 – to fructose isomerization 1621 Heck–Mizoroki reactions 414, 821 – heterogeneous hydrogenation 1625, 1629 Heck reactions 411, 415, 420, 508, 525, 540, glucosyl radicals 1117 953, 1016, 1017, 1027, 1028, 1464 glutathione – active catalyst generation 953 – flavine derivative 1572 – base-promoted elimination 953, 977 D-glyceraldehydes-3-phosphate 919 – catalyst regeneration 953 glycerol 1583 – C-C coupling 966 – 1,2- and 1,3-propanediol catalyzed – classical mechanism 954 dehydroxylation 1637 – ligand-free 964, 965 – homogeneous catalyzed valorization 1638 – stereoselectivity 974 – processing of 1583 β-H elimination 968 – telomerization of 1595 – pathway 974 glycerol phosphate oxidase (GPO) 920 hemicellulose 1615 glycol derivatives 502 hemiisotactic polypropylene 217, 218 glycolic acid 153 hemilabile ortho ether groups 359 glycosyl halides 1117 Henkel process 483 glyoximate 1154 heptadiene synthesis GlyX-motif 912 – nickel-catalyzed 1213 gold(I) catalysts 1404 n-heptane 1536 gold nanoparticles 546 1-heptene 347 grafting method 1077 – hydroformylation 47 graphite electrode 1181 – SAP catalyzed oxidation 1029 green synthesis 26 – Sasol’s conversion of 347 Index 1717 heptenes 46, 1021 homogeneous INSITETM technology 226 heteroaromatic ketones 641 homogeneous iron catalyst 728 heterocycle synthesis homogeneous liquid phase aerobic oxidation – in-situ generated alkynones, role of 1209 – catalyst optimization 480 – palladium-catalyzed 1205 – kinetics and mechanism of 474 heterocyclic carbonyl compounds 728 homogeneous nickel catalysts 196 heterocyclic primary amides 1446 homogeneous palladium catalyst heterogeneous catalysis 116, 126, 247, 1059, – alkynes, hydroformylation of 59 1069 homogeneous photocatalytic systems 1684 – for autoxidation chemistry 515 homogeneous transfer hydrogenations 730 heterogeneous hydrogenation 1586 homogeneous water splitting systems 1656 heterogeneous Ziegler catalysts 226 homogenous carbonylation reactions 91 heteropolyacids 1080 homogenous catalysts 205, 207, 1076, 1514 Hevea brasiliensis (HbHNL) 917, 918 homopolymerization 192

H2-evolving activity 1162 – of ethylene 220 H2-evolving molecular catalysts 1178 homopolymers 244 hexachloroplatinum acid dihydrate 1592 homotopic coordination sites 214 1,4-hexadiene 211 host–guest relations/self-organization, in 1,5-hexadiene homogeneous catalysis 846 – with Rh-complex 49 – artificial metalloenzymes 849 hexameric capsules 853 – cyclodextrins 847 hexamethyldisilylamides (NaHMDS) Hoveyda-Grubbs catalysts 1337

1612 5-HT2A receptor antagonists 1455 hexamethylene-1,6-diamine (HMDA) 48 Huisgen cycloaddition 868 hexamethylene diisocyanate (HDI) 1261 Hunsdiecker–Borodin reaction 533 1-hexene 46, 193, 308, 311, 313, 324 Hurtley reaction 746, 756 – Amoco process 348 hybrid catalysts 1078 – from ethylene 339 hybrid materials 1077 – in hexene fraction 340 hybrid mesoporous material 1078 – hydroformylation reaction 1033 hydantoinases 915 – hydrogenation 1044 hydration of nitriles 1445 – production 311, 342 hydrazine 730 1-hexene plant 238 β-hydride elimination 159, 243, 1204, 1401 hexene selectivity 335 hydroacylation hexoses and pentoses – alkenes 1323

– Rh(dppp)2Cl catalyzed – alkynes 1323 decarbonylation 1625 hydroamination 1379, 1380, 1397, 1404 2H,5H-dihydrofurans 55 – activation parameters 1383 high density polyethylene (HDPE) 203, 225, – of alkynes 1379 307, 308 – asymmetric intramolecular reactions 1389 highly oriented pyrolytic graphite – catalysts 1408, 1410 (HOPG) 1183 hydroaminomethylation 1585 high-throughput methods 197 hydroborations 1640 HIV protease inhibitor 1195 hydrocarbons 203, 218, 222, 1350 Hiyama–Denmark reaction 820 – forming processes 328 HMF. see 5-hydroxymethylfurfural (HMF) – oxidation 93 Hoberg-type complexes 1611 hydrocyanation 1367, 1640 homeopathic concentrations 1094 hydrodesulfurization (HDS) 1558 homogeneous catalysis 91, 127, 207, 693, 1069, hydroesterification 1587, 1588, 1590 1085, 1086, 1335 hydroformylation 25, 26, 27, 863, 874, 1004, homogeneous hydrogenation 645 1006, 1020, 1032, 1086, 1640 – of C-C double and triple bonds 720 – approach, chemical transformations 29 – of nitrogen multiple bonds 728 – aqueous-phase process 71 1718 Index

– catalysts 1094 hydroquinone (HQ) 546 – cobalt-based processes 63 hydrosilylation 736, 741, 1565, 1592 – conditions 1561 – anti-Markovnikov addition product for 737 – of fatty compounds 1587 – of carbonyl compounds 741 – of 1-hexene 1021 – of carboxamides 743 – mechanism 65 – of carboxylic acid ester 742, 743 – metal-catalyzed 1197 – catalysts 886 – 1-octene 1023 – of 1,3-dienes 737 – rhodium-based processes 26 – of imines using chiral borane 786 – sulfonated ligands 39 1,4-hydrosilylation of olefins 737 – technologies 31 hydrosilylative deoxygenations 740 β-hydrogen abstraction 330 hydrothermal method 156 hydrogenation 621, 728, 1014, 1025, 1042, hydrovinylation 1592 1583, 1605, 1608 – of fatty compounds 1584 – of alkynes 720 α-hydroxyalkyl radical intermediate 720 – biaryl diphosphines 634 cis-hydroxy-ethylene–palladium species 497 – catalytic systems/transformations, hydroxyketone 910, 1102, 1623 evaluation 622 hydroxylamine salts 1435 – of CˆC double bond 723 hydroxylation 714 – chiral anions 642 – of alkanes 1536 – C=N bonds 632 – of benzene 715

– of CO2 1609 – of 2-ethoxycarbonyl-1-oxo- – of CˆO< Bonds 724, 730 cyclopentane 706 – cooperative catalysis 642 – palladium-catalyzed 457 – established ligand classes 634 α-hydroxylation of a steroidal cyclic ether 1531 – of esters 645 hydroxyl function 1106 – ligand development 633 hydroxyl radical 475 – novel design principles 641 5-hydroxymethylfurfural (HMF) 1618, 1620, – olefins 625, 720 1623 – phosphine ligands 638 2-hydroxy-4-methyltetrahydropyran – rare earth metal catalysts 764 (MHP) 57 – self-assembling monodentate ligands 641 hydroxy nitrile lyase (HNL) 901, 902, 917 – of short-chain fatty acids 1583 (2S,4R)-4-hydroxyproline 757 hydrogen-bonding 857, 1002, 1511, 1530 hydroxypropylated β-CD (HP-(-CD) 849 hydrogen cyanide (HCN) 899, 917 N-hydroxypyridine-2-thione esters 533 β-hydrogen elimination 1366 8-hydroxyquinoline (8-HQ) 549, 550, 759 hydrogen evolution reaction (HER) 1180 hyperconjugation 1528 hydrogen liberation 1443 hypervalent iodine compounds 1436 hydrogen peroxide 715, 1590 hydrogen transfer 207 i – catalysis 894 ibuprofen 147, 1531 hydrohalide salts of amines 1432 – synthesis of 147 hydrolases 910 imidazole skeleton 814 hydrolysis 1512 imidazoline 1102 – of peptides 913 imidazolin-2-iminato complexes 1341 hydro-oligomerization 219 imidazol(in)-ylidene 812 hydrophilic/hydrophobic compounds 863 imidazolium 1055, 1077 hydrophilic isocyanide ligands 1664 imidazolones 1469 hydrophilic ruthenium catalysts imine hydrogenation, by intramolecular – with sulfonated phosphine ligands 1606 FLP 777, 785 hydrophobic interactions 1538 imines hydrophobic oligopeptide 911 – asymmetric transfer hydrogenation of 735

hydrophobic reactant 864 – B(C6F5)3-catalyzed hydrogenation of 778 Index 1719

– with carbon monoxide, copolymerization – thiolation 897 of 172 3-iodoindazoles 1453 – ligands 1154 iodolysis equilibrium 108 iminoamination and hydrazination of alkynes iodomethane oxidative 1561 – titanium-catalyzed 1214 ionic hydrogenation 648, 724 iminopyridine 737 ionic liquid 1002, 1004, 1045, 1047 immobilization 1045 – crystalline 1031 – by ionic interaction 1514 – loading 1048 – on magnetic mesocellular mesoporous – solvent 115 silica 1514 ionic strength 109 – of osmium catalysts 1514 ion-paired chiral ligand 860

– of reoxidant, NaIO4, on wet silica 1517 ion pairing-directed self-assembly 860 immobilized catalyst 373 Ir catalyzed hydrogenation 639 indazolone 760 Ir-chiral diphosphine complex 1302 indium phosphite (InP) 1667 Ir-cobaloxime photocatalysts structures indole N-carboxamides 1471 1679 indoles 1103, 1478 iridium complexes 639, 1138 – decarboxylative C–H arylation 542 iridium pincer complexes 894, 895 – three-component synthesis 1479 iron-based molecular catalyst systems indolones 1472 – for photocatalytic H2 production 1659 industrial carbonylations 93 iron bleaching catalysts 522 indylidene ruthenium complexes 1641 iron-borohydrido-hydride complex 721 inert solvents 1265 iron carbonyl catalyzed reduction, of infrared spectroscopy 33, 109 carboxamides 742 inorganic co-catalyst 155 iron catalysis 196, 744 insertion barrier difference 970 – asymmetric cis-dihydroxylation 1521 in-situ – hydrogenation 721, 730 – azomethines, palladium-catalysis, role – hydrosilylation 737 of 1208 – oxidation 693, 702, 719 – generation of chiral diborane catalyst 781 – with predictable selectivity in aliphatic – isomerization 1038 C-H oxidation reactions 1527 – oxidation 1512 – primary amide formation 1454 – polymerization 222, 223 – reduction 693 in-situ generated RuO4 iron-catalysts 241, 257, 1521, 1526, 1527 – alkanes catalyzed, selective oxidation of 1534 – electrocatalytic water oxidation 1146 intellectual property 1089 – for hydrogenation interceptive decarboxylative allylations 539 – precursor for linear ethylene intermolecular polymerization 242 – carbonylation 139 – system 726 – hydroacylation 1327 iron catalyzed reductions, using – hydroamination 1380 organosilanes 736 – reaction, Ru-catalyzed 1294 iron complexes 721 intersystem crossing (ISC) mechanism 544 – containing carbenes 735 intramolecular – containing tridentate nitrogen ligands 736 – aminocarbonylations 1455 – with tetradentate ligands 734 – C-O bond formation 455 iron cyclohexene 1102 – cyclization 1198 iron(II) sulfate 714 – [3+2] cycloaddition 1466 iron-porphyrin system 732 – hydrosilylation reaction 1570 iso-aldehyde 41 – N-arylation 1478 isoblock polypropylene 218 – nucleophilic cyclization 1199 isobutene 192 iodide dissociation 100 isobutylaluminoxane 210 iodobenzene 1027, 1028, 1052 iso-butyric acid 76 1720 Index

isochroman-3-one synthesis of 148 – asymmetric hydrosilylation of 739 isocyanate meso ketones 1494 – complex 1273 β-ketophosphine 352 – isolation 1262 kinetic isotope effect 136 – trapping of 1265 kyotorphin (Tyr-Arg) 913 isoheptenes 335 isoindolinones 1468 l isomerization 213, 881, 1030, 1339 LA. see levulinic acid (LA) – cis-trans isomerization 962 β-lactam 1102 isomerizing dehydrogenative silylation 1641 β-lactam peptide antibiotics 914 isomerizing hydroformylation 42 lactate dehydrogenase (LDH) 921 isononanols 335 lactococcal multidrug resistance Regulator isooctenes 335 (LmrR) 851 isoprene 1073 lactones 1102, 1513 – hydroformylation of 49 lanthanide 1071 isopropanol 730, 735, 1048 – catalysts 269, 271, 1379 isopropylbenzene 467 – ligands 1103 isoquinoline derivatives 757, 1466 – triflates 1635 – three-component synthesis 1474 lapatinib 426 isoselective polymerization L-leucine 904 – of styrene 200 leukotriene A4 hydrolase inhibitor isosorbide 1630 DG-49B 759 isotactic and atactic polypropylenes 213 levulinic acid (LA) 1626 isotactic-atactic stereo-gradient 199 – hydrogenation 1628 isotactic polymers 169, 176, 212, 214 – lignocellulosic, formation by 1626 isotactic polypropene 199 – reductive amination 1629 isotactic polypropylene 193, 194, 195, 196, 212, Lewis acidic late transition-metal 217 complexes 1379 isotactic polystyrene 200, 202 Lewis acidic metal 1409 itaconic acid derivatives 1086 Lewis acidic surface site 1502 – synthesis 1086 Lewis base 970 ivabradine hydrochloride 435 ligand-enabled palladium-catalyzed 435–460 ligands j – Buchwald–Hartwig amination 823 Janus catalyst 1157 – classification of 831 Johnson Matthey Synetix 631 – data banks 1087 Jolly–Beller mechanism 369 – design 1526 Josiphos-type ferrocenylphosphine – electronic influence 810, 970 ligands 443 – free palladium 420 – Heck–Mizoroki reaction 820 k – Hiyama reactions 819 Keltan ACETM polymers 232 – cis-ligand insertion reaction 492 ketene 1103 – Kumada–Tamao–Corriu (KTC) – acetal 976 reaction 816 – intermediate 1102 – metal combinations 197 ketimide complexes 231 – metathesis 824 ketimines 743 – Negishi coupling 816 – asymmetric reduction of 735 – NHC-metal complexes 814 ketocarbamates 1469 – N-heterocyclic carbenes via imidazolium keto–enol tautomerization 911 salts 813 ketones 1528, 1533 – reductive desulfurization/α-elimination 814 – alcohol 510 – Sonogashira reaction 819 – α-arylation of 757 – steric influence 969 Index 1721

– Suzuki-Miyaura reaction 822 MALDI-TOF mass analysis 172 – synthetic pathways 812 malonates, arylation of 754 – telomerization 826 manganese(III) complexes 1538 light-driven H2 generation manganese(III)-porphyrin system 1538 – schematic presentation 1657 manganese/iron bleaching catalysts 519 lignin 1581 – bleaching processes 519 – depolymerization 1631 – iron-based bleaching catalysts 522 lignocellulose 1615 – oxidation catalysts 520 lignocellulosic biomass manganese(V)-oxo unit 1538 – conversion into levulinic acid 1626 Manihot esculenta 917 – derived products 1616 Mannich-type addition 1196 limonene 49 D-mannose 866 linalool hydroformylation 1025 Markovnikov addition 134, 853 linear alkenes Markovnikov insertion 1366 – Brookhart and Goldman’s Markovnikov’s rule 135, 502 dehydroaromatization 895 MAS-NMR analysis 1060 linear alpha olefins (LAOs) 307, 309, 324, 341 Matsuda reaction 415 linear fat aldehydes 1587 MCR. see multi-component reaction (MCR) linear low-density polyethylene (LLDPE) 210, Menger model 868 225, 226, 307, 308, 339 ()-menthyl acetate 1528 – resins 341 4-MeO-1,10-phenanthroline 1269 linoleic acid 1582, 1584, 1592 3-mercaptopropionic acid (MPA-CdTe) 1664 linoleic acid methyl ester 1584 mesoporous silica materials 1002, 1078 linolenic acid 1592 metabolic instability 431 lipases 910, 911, 912 metal-based oxidant 1534 – esterase-catalyzed hydrolysis 911 metal–carbon bonds 219, 249 – lipase B 912 – protolytic cleavage 1397 lipids 1581 metal carbonyl catalyzed reactions 1098 liquefied petroleum gas (LPG) 332 metal catalysts 199, 245, 1538 liquid films 1000, 1003 – bearing chelating ligands 193 liquid–liquid two-phase separation 161 – dithiolene ligands 1175 liquid phase hydrogenation reactions 1051 – recycling 459 liquid phase oxidation 479 metal-catalyzed decarboxylation 479, 480 – with air/oxygen 509 metal-catalyzed hydroborations 1640 – deactivation mechanisms 480 metal-catalyzed isomerization 1198 lithium acetate 101 metal-catalyzed oxidative coupling of lithium iodide 100, 108 CO2 1610 LLDPEs 225, 227 metal catalyzed rearrangement 1450 – production 311 metal cation low density polyethylene (LDPE) 203 – Lewis acidity 1409 lower critical solution temperatures metal-directed self-assembly 859 (LCST) 877 metal hydrides 1071 low-pressure oxo processes (LPOs) 30, 73 – bonds 243, 1401 low throughput screening 1085 metal–hydrogen bond 570 low-water acetic acid process 95 metallacycles 1211, 1271 lubricants 1583 metallocyclobutane 1073, 1334 metallocyclononane 314, 317 m metallocyclopentadienes 316 macrocyclic cobalt(II) complex 1675 metallic palladium 1030 macrocyclic oligomers 1349 metal–ligand combinations 198 macrocyclic tripeptides 1549 metal–ligand coordinative bond 852 macrocyclization 1344 metal–ligand interactions 853 magnetic nanoparticle synthesis 1056 metallocene 208, 211, 214, 224 1722 Index

– catalysts 199, 206, 207, 217, 218, 220, 227, methyl iodide 114 245 methyl (4-phenylphenyl) ketone 738 – complexes 217 methyl linolenate 1638 metalloporphyrins 1537 methyl methacrylate 92, 126 metallorganic catalysis 203 N-methylmorpholine (NMM) 1514 metal–metal multiple bond 318 2-methylnaphthalene 717 metal nanoparticles 1078 2-methyl-1,4-naphthoquinone (MNQ) 544 metal–nitrogen bond 1401 5-methylnicotinamide synthesis 1457 metal–organic frameworks (MOFs) 1077, methyl nicotinate esters 651 1078 methyl nonyl acetaldehyde (MNA) 47 metal oxidation 1309 methyl N-phenylcarbamate (MPC) metal oxygenation 1509 1268 metal peroxo species 1487 N-methyl-N-(trimethylsilyl)trifluoroacetamide metal polypyridine catalysts 1165 (MSTFA) 743 metal precursors 624 methyl oleate 1588 metal to ligand charge transfer (MLCT) – ethenolysis 1348 – transition 1111 – hydrogenation 1644 i metathetic catalytic systems 1335 2-methyl-1-pentene (Al Pr3) 329 methacrylate 199 methyl phenyldiazoacetate 885 methane 208 methyl propanoate 122 methanol 1583 methylpyridinium iodide 116 – activation barrier, effect on 976 meso1-methylpyridinium-4-yl groups 1172 – carbonylation 92, 93, 99, 1041 methyl pyruvate, hydrogenation 1050 – to gasoline (MTG) technology 1615 methylrhenium trioxide (MTO) 548, 1514 methanolysis 138 methyltrioxorhenium (MTO) 1514 methoxyacrylates 142 methyl vinyl ether – formation, using palladium complexes – regio-determining insertion 973 143 micellar catalysis 863 methoxycarbonylation 118, 126, 134 – aqueous-micellar solutions 863 methoxy compound 1280 – catalytic reactions in aqueous-micellar methoxyethylamine 1432 solutions 869 methyl 2-acetamidoacrylate – homogenous catalyst complexes 872 – Rh-catalyzed hydrogenation 858, 860 – micellar effect 866 methyl acetate carbonylation 95, 96, 107, 113 – reactant solubilization 863 methyl acetoacetate, enantioselective – solid-supported catalysts 875 hydrogenation 1049 micellar enhanced ultrafiltration (MEUF) 869, methylaluminoxane (MAO) 206, 207, 208, 210, 873 248 – continuous reaction and separation N-methylamides 1429 process 874 methylaromatic compounds 482 micellar media 1497 methylated β-cyclodextrin 1561 Michael addition 851, 1470 methyl benzoate – cyclization/coupling 1206 – hydrogen drop 672 micro-porous solids 1000 methyl benzoate esters 1437 microwave irradiation (MWI) 1429 methyl benzyl ethers 741 migratory insertion 968, 1287 methyl carbamates 153 mimicking disulfide linkages 1170 methyl crotonate 127 Miyaura coupling 823 methylcyclohexane 1127 Mizoroki–Heck reaction 1052 methylenecyclopropanes 1387 Mn(III)-salen catalyst 1624 methyl esters 1583 mobile phase 1051 methyl formate 114 M-O bonds 1071 methyl heptenone 1370 MoIV-oxo complex 1171 N-methylimidazole 758 molar ratio 221 Index 1723 molecular catalysts 1179 naphthalene derivative 1099 molecular oxygen 154 2,6-naphthalenedicarboxylic acid 486 molecular single-site electrocatalysts Naproxen 415 – immobilization 1177 natural fats 1581, 1582, 1636 molybdenum 1338 natural oils 1582 molybdenum carbene 873 Negishi reaction 429 molybdenum hexacarbonyl (Mo(CO)6) 1454 – cross-coupling reaction 412, 430, 816 molybdenum polypyridine complexes 1165 neutral monophosphine pathway 964 monodentate phosphine ligand 957 N-heterocyclic carbenes (NHCs) 740, 811, 813, – reaction rate, ligand dissociation, effect 824, 1439, 1544 of 959 – aryl groups 366 monoligation 366 – complexes 367, 810 monolignans 1630 – palladium complexes 366 monomer concentration 213 – phosphine complexes 820 monooxygenase enzymes 906, 1486 – steric and electronic properties 809 monophosphine ligands 350 – syntheses of 809 MonoSPANphos 364 – thioether ligands 1565 monotelomers 1595 NHSi-complexes monoxantphos 360, 361 – for hydrosilylation of carbonyl Monsanto process 98, 99, 1041 compounds 740 – high water process 102 N-hydroxyphthalimide (NHPI) 518 – methanol carbonylation 1560 nickel 111 morpholine 1111 nickelalactones [Ni((CH2)2CO2)(ligand)] 1611 Mortreux catalysts 1341 nickel catalysts 220, 269, 1162, 1175 MPC. see methyl N-phenylcarbamate (MPC) – electrocatalytic water oxidation 1145 MTG. see methanol to gasoline (MTG) – grafted on carbon nanotube 1185 technology – modified electrodes 1186 Mukaiyama system 1486, 1487, 1488 nickel catalyzed amide formation 1450 multiblock copolymers 240 nickel catalyzed dimerization 329 multicomponent carbonylation nickel catalyzed hydrocyanation 858 reactions 1199, 1202 nickel complex 245 – chiral ligands, role of 1211 – diazadiphosphine complexes 1184 – metal catalyzed 1197 nickel ferrite nanoparticle 1429 multicomponent cross-coupling nickel(II) complexes chemistry 1203 – based on bis(imino)aryl pincer ligands 269 multi-component reaction (MCR) 1463 – bearing 2-(N-arylcarboximidoyl chloride) multicomponent syntheses quinoline ligand 269 – metal-catalyzed 1196 – pyridylbis(imine) complexes combined with multiple C–H activation 229 EASC 269 multiwalled carbon nanotubes nickel pincer complex-catalyzed (MWCNTs) 221, 222, 1141, 1182 processes 896, 1157 myrcene [Ni(CO)3(phosphine)] 835 – ligand dependent regioselectivity 50 Ni(diimine) catalysts 241 NiFe 1149 n nifedipine 1195 Nafion film 1180 NiFe-H2ase 1147, 1149, 1559 Nafion membrane-coated electrode 1140 Ni-modified electrode 1187 nanocomposites 221 nitrenes 1310 nanofiltration 1343 nitrilases 914 nanoparticles 1070 nitrile coupling – controlled growth 1078 – co-operative zinc triflate and hydroxylamine nano-scale magnetite powder 534 hydrochloride catalyzed 1447 NAPHOS-type diphosphine ligand 36 – platinum catalyzed 1447 1724 Index

nitrile hydration α-olefin – heterogeneous cerium(IV) oxide and – polymerization 199

Au/TiO2 catalyzed 1446 olefin block copolymer (OBC) 238 – zinc nitrate catalyzed 1445 olefin complex nitrobenzene – base-promoted formation 977 – carbonylation 1267 olefin insertion energy 972 – deoxygenation 1272 olefin insertion polymerization – SILP catalyzed carbonylation 1043 – post- and non-metallocenes for 225 nitrogen nucleophiles 1466 olefin isomerization 1367 – coupling of aryl halides with 750 olefin oxidation 490 nitrogen oxides 1593 olefin polymerization 233, 235, 331 4-nitropyridine N-oxide (NPNO) 1512 Olefins Conversion Technology (OCT) 1375 nitroxide radical coupling (NRC) 1550 oleic acid 1582 NMR spectroscopy 200, 1080, 1533 oleochemicals 1581 noble metal catalysts 1264 oleochemistry 1583 NOESY NMR spectra 1566 oleoyl alcohol 1021 non-alternating ethylene/CO copolymers 157 oligo(ethylene oxide) (EO) 877 non-aqueous ionic liquid (NAIL) 334 oligoketones 169 non-chiral metallocenes 212 oligomerization 214, 227, 1583, 1594 non-heme iron(II) complexes 714 – styrene, with nickel cations 202 non-metallocenes 194 oligomers 218 – catalysts 199 Oppenauer oxidation 1625 – metal complexes 226, 248 optical clarity 207 – structure 191 organic–inorganic hybrid materials 1077 non-oxidative coupling 1076 organic peroxycarboxylic acids 1486 non-regioselective catalysts 335 organoaluminium compounds 200, 205 non-symmetric phenanthrolines 1271 organomagnesium compound 257 nonvolatile ionic liquid 1608 organometallic catalysis 953, 1438 norbornene 170, 192, 219, 220, 221, 1106, 1288 organometallic catalysts 251, 693 normal lactone (NL) 1495, 1496 organometallic complexes 197, 1073 Novartis discodermolide synthesis 1091 – grafting 1070 Noyori’s ruthenium complexes 656 organometallic compounds 1097 Nozaki-Hiyama-Kishi reaction 1568 organosolv method 1630 nucleophilic complexes 107 osmate esters 1520 nucleophilic elimination 136 osmium 1509, 1521 nucleophilic reagents 137 – catalyzed dihydroxylation 1509

OsO4 dihydroxylations 1510 o Os(VIII)-glycolate 1509 octene 26 Os(VI)-monoglycolate 1509 1-octene 46, 192, 199, 211, 224, 233, 308, 311, oxamides 153 313, 324, 826 α-oxamination 1112 oils 1581 – organo- and photoredox-catalyzed 1113 – valorization 1638 oxazolidinones 151 olefin 149, 177, 233, 414, 627, 1323, 1509 oxidation 1017, 1029, 1054, 1517, 1528, 1590, – enantioselective hydrogenation of 625 1594 – epoxidation 512 – alkanes 1536, 1538 – hydroarylation of 1318 – allylic and benzylic sp3 C-H bonds 1525 – hydroformylation 57, 855 – aromatic C-H bonds 714, 717 – hydrogenation of 627 – chiral tertiary C-H bonds 1531 – physical properties 177 – cyclic alkanes 1532 – polymerization catalysis 224, 232 – pentacyclic triterpenoids using – α-selective arylation 970 t-BuOOH 1535 – (Z/E)-isomerization 41 – products of glycerol 1594 Index 1725

– secondary alcohol 719 palladium-catalyzed oxidative – unsaturated fatty compounds 1590 carbonylation 155 oxidative addition palladium chloride 344 – dissociative transition state 956 palladium complexes 199, 245 oxidative alkyne carbonylations 139 palladium hydride 120 oxidative amidation of aldehydes 1442 palladium(II) complex 437 oxidative arylation processes 541 palladium-mediated telomerization 809 oxidative carbonylation 1262, 1263 palladium pincer complex catalysts 891 – amines 152, 153 palladium trifluoroacetate 540 – amino alcohols 154 palladium/triphenylphosphine catalyst – anilines 151 349 – transition metal-catalyzed 149 palm oil 1581 oxidative cleavage 1517 parathion (E603) 867 oxidative couplings 370, 1342 partial oxidation (POX) 40 oxidative cyclization Pauson–Khand reaction 118 – aminoalcohols 1512 – mechanism 1287 oxidative decarboxylative couplings 540 – non-cobalt mediated/catalyzed 1293 oxidative photocatalysis 1114 P chiral ligands 637 oxidative quenching Pd- and Pt-catalyzed arylation 840 – by direct electron transfer 1662 penta-coordinate Pd-species 960 oxidized carbon nanotubes 221 pentadentate ligands, with iron 523 oxidizing agents 1515 pentadentate N-ligands 711 oxidizing reagents 1525 pentenenitrile 1367 oxidoreductases (EC) 903 peptidases 913 oxime formation 1551 peptide chemistry 1535 oximes, Beckmann rearrangement of 1452 perfluoroalkyl 171 oxonation 27 peroxodiiron(III) complexes 716 oxo processes 76 peroxomolybdenum complex 1487 oxo reactor 67 peroxy acid 1485 oxo synthesis 25 – thermal decomposition 477 oxyfunctionalization 465 peroxycarboxymidic acid oxygenases 906 – in-situ generation of 1502 ozonolysis 1645 petrochemicals 1583 petroleum-based fuels 1656 p phase separation 73, 869 Paal–Knorr cyclization 861 phase-switchable polyoxometalate (POM) palladium 826, 1018 882 – catalysis 745 phase-transfer catalysis 1000 – catalysts 157, 220, 247 phenol hydroxylation processes 546 – higher oxidation states 891 phenol oxidation processes 546, 547 palladium–carbon bond 131, 1203 phenols palladium catalyst system 1588 – arenes, conversion in to 1633 palladium-catalyzed alkoxylation 443 – hydrogenolysis of 1634 palladium-catalyzed allylic substitution phenothiazines 1207 reactions 431, 1565 phenoxyimine catalysts 237 palladium-catalyzed coupling reactions 411, 413 phenoxyimine complexes 235 – advantages 413 phenoxyketimine ligands 194 – of five-membered heteroarenes 536 phenoxyoctadiene 344 – for large-scale production 434 phenylacetic acid 1428 palladium-catalyzed cross coupling phenylacetylene 730, 1122, 1124, 1407 reaction 411, 414, 429, 435, 1464 phenyl alanine dehydrogenases 904 palladium-catalyzed decarboxylative Heck 4-phenylbutyric acid 1430 reaction 540 phenylmethylenecyclopropane 1726 Index

– ring opening of 1387 photochemical redox catalysis 1111 phenylpalladium(II)-diimine complex 971 photochemical transformations 1097, 1104 phenylphosphines 840 photocycloaddition 1100, 1106, 1115 pheromones 1110 photodimerization 1106 Phillips chromium-based ethylene photoelectrochemical catalysis 1110, 1111 polymerization catalyst 308 photoinduced water oxidation 1657 Phillips pyrrolide system 341 photoredox cycle 1121 phosgenation photosensitizer (PS) 1656, 1657, 1668 – with homogenous tertiary amine phthalide 478 catalyst 278 phthalocyanine 716, 1181 phosgene 1230, 1261 physical adsorption 1000 phosgene hydrolysis 274 Pichia pastoris 913 phosphabicyclononanes 34 2-picolinic acid 757 phosphanes. see phosphine pig liver esterase (PLE) 913 phosphate buffer solution (PBS) 1140 pincer complexes 889 phosphine 106, 346, 811, 829 – generic structure 889 – based catalysts 366 pincer SNS ligand – containing complex 707 – deprotonation 1566 – σ-donation ability 810 plasticization 251 – free complex 1297 plasticizer alcohols 91 – ligand 127, 638, 729, 1010, 1443, 1659 platform chemicals 1617 phosphine-palladium-diolefin complexes 359 platinum 125, 1592 phosphinimide catalysts 228 platinum group metal (PGM) 1447 phosphinooxazoline (PHOX) ligands 1490 platinum terpyridylphenylacetylide complex 1668 phosphino-phosphine sulfides 1560 platinum tetrachloride 1592 phosphite ligands 839, 840 PMMA monomer methyl methacrylate 51

phosphite P(OMe)3 ligand 636, 1559 P-N ligands 324 phosphites 29P NMR spectroscopy 835 – hydrolytic stability 844 P-N-N terdentate ligand 352 – synthesis 840 P–O bonds 840 phospholane 1092 – hydrolysis 843 phospholane-type diphosphines 636 polar monomers 772 phospholane type ligands 626 polyamides 1446 phosphole catalyst 228 polybutadiene 249, 272, 771 phosphonate functionalized complex 1161 polycarbonates 225, 273, 281 phosphonate groups 1139 polycondensation route 277, 1582 phosphonic acids 1267 polycyclopentene 218, 219 phosphonium salts 114 polydentate ligands 833 phosphonous acid 830 polydicyclopentadiene 225 phosphoramidites 636, 1087 polydispersities 200 – synthesis 842 polyesters 26 phosphorus ligands 837, 838, 843 polyether carbonates 283 – in homogeneous catalysis 828, 829 polyethylene (PE) 203, 206, 207, 209, 211, 319 phosphorus-sulfur ligands 1561 – characteristics of 211 photocatalysis 1098 – production 309 photocatalyst 1097, 1682 – Ziegler catalyst 203

photocatalytic H2 evolution 1665 poly(ethylene glycol) (PEG) 849, 905 photochemical alkoxycarbonylation 125 poly(ethylene terephthalate) (PET) 465, 470 photochemical decarboxylations 537 polyethylenes photochemical electron transfer mediated – unit cells 173 reactions 1108 polyketones

photochemical H2-evolving reaction 1677 – chemical transformations of 176 photochemical H2 generation processes 1662 – crystal structures of 173 Index 1727

– synthesis 158 pre-reactive complexes 958 polymer design 224 Prilezhaev reaction 1645 polymeric monoliths 154 primary amides polymerization 191, 194, 201, 204, 208, 210, – from oximes 1451 222, 223, 227, 242, 243, 244, 1073, 1338 – from aldoximes. 1449 – active sites, surface of nanofibers 222 primary amides, transamidation of – butadiene 245, 251, 252, 263 – hydroxylamine hydrochloride – catalysts 197, 198, 235 catalyzed 1436 – of cycloolefins 218 primary amide synthesis – ethylene 203, 209 – from alcohols 1450 – olefins 203, 207 – via aminocarbonylation of benzyl and allyl – polycarbonates 274 chlorides 1454 – propylene 235 primary amino-alkenes – of styrene 200 – intramolecular hydroamination of 1392 – technology 233 Proactinomyces erythropolis 908 – temperature 213, 241 product selectivity 354 polymerizing α-olefins 191 L-proline 1436 – cis-1,4 polymers 250 propane dehydrogenation (PDH) 45 polymethylbenzene 474 propargylic carbonates 1466 polynorbornenes 219, 245 propene 204, 213, 220, 221, 224, 1040 polyolefins 203, 224, 225, 248 – dimerization 330 – nanocomposites 221 – hydroformylation 44, 1005, 1035 – production 225 – hydrogenation 1047 polyoxometalate (POM) 1054, 1141, 1532 – mechanism of isotactic polymerization 215 polyoxotungstate 1533 prophos 1093 polypeptides 172 n-propylamine 1386 polypropylene (PP) 192, 196, 203, 206, 218, propylene 192, 194, 196, 335, 1349 223, 225 propylene-ethylene copolymers 233 – microstructure 205, 213 propylene oxide 467, 1019 – properties of 217 propyne carbonylation 127, 139 – pseudo-enantiomers of 166 prostenoid – various metallocene catalysts 213 – rapid synthesis 1204 polypropylene matrix 222 ProsulfuronTM 415 polypyridyl ruthenium 1137 protease inhibitor 1343 polypyrrole 506 protic solvents 112 polystyrene 200 proton-coupled electron transfer (PCET) polysubstituted furans 1478 1174 – three-component synthesis 1478 protonolysis 132 polysubstituted phenol synthesis 1214 proton reduction 1135, 1657 N-poly(tetrahydrofuran) ligand 883 proton transfer 135 polyurethanes 283, 467 Prunus amygdalus 917 poly(vinyl chloride) (PVC) 45 Pseudomonas cepacia 912 porcine pancreatic lipase (PPL) 912 Pseudomonas chlororaphis B23 914 pore diameters 1000 Pseudomonas putida 910 porous solids, classification of 1001 push–pull complex 962 porphyrin 1538 push–pull stabilization 812 porphyrin pyrene-functionalized nickel complexes 1186 – ligand 1536 pyrethroids 918 Portnoy model 868 pyridazinone 761 positive charge delocalization 968 – arylation of 759 post-metallocene catalysts 191, 1387 pyridine derivative 1099 precursor screening 1059 pyridine formation 1099 Prelog-rule 903 pyridine-imine ligands 1166 1728 Index

pyridine N-oxide (PNO) 1512 reductive carbonylation 1262 pyridoxyl-5-phosphate (PLP) 920 – ruthenium catalyzed 1273 pyridyl-amido catalysts 232 reductive coupling

2-pyridyldiphenylphosphine (2-PyPPh2) 127 – three-component nickel-catalyzed 1212 pyridyl group 132 reductive dicarbonylation 140 pyridylphosphine 137 reductive elimination pyrophoric metal hydrides 645 – palladium-carbon bond, role of 1206 pyrrole-based tetraphosphoramidite 36 reference complex 962 pyrrolidines 1382 regiochemistry 971 – cis-pyrrolidines 1512 regioisomers 1100, 1287 pyrrolyl ligand 1076 regioselective catalysts 1526 pyruvate decarboxylase (PDC) 922 regioselective coupling 969 – C-C coupling 966 q regioselective dimerization quantum chemistry calculations 954 – of propene 333 η3 quasi-tetrahedral transition state 961 – of propylene 335 quinuclidine 1512 n-regioselective hydroformylation 42 regioselective oxidation 1531 r n-regioselective Rh-catalyzed rabbit muscle (RAMA) 919 hydroformylation racemic alkyl-substituted cyclic ketones – catalysts 888 1488 – multidentate ligands 38 racemic products 1510 regioselectivity 966, 1318, 1335, 1398 racemization 1098 – characteristics of 370 radical addition of glycosyl bromide, – electronic control 972 photoredox induced 1118 Reppe process 119 radical cation 1113 resveratrol 420 radical chain oxidations 508 reusable heterogeneous catalysts 1446 – alkyl nitrite 514 reverse biomimetic reduction approach 727 – homogeneous catalysts for reversible polymeryl chain transfer 199 autoxidations 513 Rh-BINAPHOS catalyst 60 – hydrocarbons, autoxidation mechanism 510 Rh-BIPHEPHOS catalyst 52, 55 – industrial processes 508 Rh-catalyzed asymmetric hydrogenation 831, radical (SET) pathway 1521 832 radiofrequency heating 1429 Rh-catalyzed heterocycle alkylation Raney-Nickel 845, 1584 reactions 1323 rapid intramolecular cycloalkylation 1210 Rh diphosphine catalysts 38, 630 rare earth metal catalysts 764, 1382 Rh-driven processes 67 – hydrogenation 764 rhenium complexes 1314, 1661 – hydrosilylation, hydroboration, and rheological measurements 212 hydrostannylation 765 Rhizomucor miehei 912 reaction rate constant 1018 rhodamine dye 1674 reaction zone 1008 rhodium 1010, 1040 reactive gases 1085 rhodium carbonyl clusters 1092 reactor models 224 rhodium catalyst 32, 1445, 1565 reactor void volume 1004 – hydroformylation 31, 833 Re complexes rhodium complexes 99, 1125, 1297, 1315, 1325 – for BV reaction 1492 rhodium hydride 1021 redox active co-catalyst 1264 rhodium trichloride hydrate 1584 redox carbonylation 1262 Rhodococcus rhodochrous 914, 915 redox mediator Rh-SILP catalysts 1032, 1047, 1052 – on water oxidation 1139 – hydroformylation 1040 reductive amination 1620 ricinoleic acid 1582 Index 1729

rilvipirine 415 ruthenium hydrido-BH4 complexes 678 ring bromination 487 ruthenium(II)-TriPhos complexes 647 ring-closing metathesis (RCM) 824, 873, 1343 ruthenium(IV) complex 1535 ring-opening metathesis (ROM) 873 ruthenium-metathesis catalysts 888 ring-opening metathesis polymerization ruthenium nanoparticles 1621 (ROMP) 225, 245, 824, 1641 Ru(VIII)-glycolate 1517 ring-rearrangement metathesis (RRM) 824 Ruxolitinib 426 Ritter reaction 1449 RX oxidative addition 954 – catalysts 1451 – computational studies 955 Roche ester 61 ROMP. see ring-opening metathesis s polymerization (ROMP) saccharides 1581 Ru–biaryl diphosphine complexes 623 sacrificial alkene 1640 Ru catalysts activity 1338 – norbornene 1640 Ru catalyzed reaction 1294 salalen titanium complexes 195, 237 Ru-cobaloxime structures 1679 salicylaldehyde 233 Ruhrchemie–Rhône-Poulenc process 74, 1020 salicylaldiminato complexes 235 Ru-NHC complexes 825 sandwich zirconium complexes 192

RuO4-catalyzed dihydroxylation 1515, 1516, SAP catalyst 1020, 1021, 1027 1517 – performance 1023 – of allenes 1517, 1519 Sasol PNP tetramerization system 323, 342 – vicinal dihaloalkanes, leading to 1,2- scaffold phosphine ligands diketones 1519 – aryl-heteroaryl and heteroatom-

RuO4-catalyzed ketohydroxylation 1520 incorporated 446 RuO4-catalyzed oxidative cyclization Sc aminopyridinates 772 – of 1,5-dienes 1519 scandium triflate (Sc(OTf)3) 1432 – of 1,6-dienes 1520 scandium-tris(trifluoromethanesulfonate),

Ru pincer complexes 893, 1438 Sc(CF3SO3)3 506 Ru-Rh photocatalysts 1680 scanning tunneling microscopy (STM) 1558 Ru-SILP catalyst 1055 Schiff base ligands 233, 520, 708, 1277, 1342 – asymmetric hydrogenation 1049 Schlenk-technique 829 ruthenium 113, 1509, 1515, 1521 Schrock-type catalysts 1339 – common metathesis reactions catalyzed 825 Schulz–Flory distribution 347, 348 ruthenium carbene complexes 225, 1054 – product distribution-afflicted processes 311 ruthenium catalyst 1340, 1535, 1606 sclareolide 663 – BIAR 627 SCRAM catalyst 1440 – dihydroxylation with hydrogen sealing temperature 207 peroxide 1520 secondary phosphine oxides (SPOs) 638, 843 – dioxygenation of olefins 1515 selective alkyne tetramerization 316 – Ir-based 1138 selective ethylene tetramerization – with NHC spectator ligands 825 – binuclear mechanism 317 – oxidative cyclizations 1517 selective hydrogenations 1584 – ruthenium-catalyzed azide-alkyne selective terminal functionalization cycloaddition (RuAAC) 1548 reaction 1638 – terpyridine ligands 1141 selenium compounds ruthenium complexes 506, 1535 – carbamoyl compound 1280 – with bidentate and tetradentate amino- – toxicity 1279 phosphine ligands 663 selenium(IV)-methoxy complex 1280 – polypyridine complexes 1111, 1675 selenium-modified rhodamine dyes 1674 – salen complex 1122, 1123 self-assembled PSI–cobaloxime hybrids – TPPS complex 1608 1677 ruthenium-diiron dyads 1664 self-assembling ligands 641, 1681 ruthenium hydride species 1072 SEM-EDX dot scans 1061 1730 Index

sensitizer 1097 – copolymer 169 serine hydrolases 913 – polypropylene 218 seven-membered ring intermediate 1102 – polystyrenes 202 Sharpless–Katsuki epoxidation 1645 stereoregular Shell higher olefin process (SHOP) 32, 48, 352, – alkene 164 1368, 1590 – polybutadienes 249 – ligand-modified, cobalt-based process 70 – structure 205 Shell patents phosphinites 374 stereoselectivity 198, 236, 973, 1319 Shing dihydroxylation 1516 – catalysts 198, 199, 1526

Shvo catalyst 1623 – Cs-symmetric metallocenes 217 silanol groups 1002 – β-elimination 975 silica chemisorption 1010 – hydroformylations, chiral ligands 39 silica gel 1033 – oxidations 1122 silica materials 1070 – polymerization 199, 213, 215 silicotungstate catalytic system 1493 steric factors 1527, 1535 silicotungstate polyoxometalates 1491 steric hindrance 106, 360, 1536 siloxane bridges 1070 stirred tank reactor 110

silver(I) iodate (AgIO3) catalyst 1441 cis/trans-stilbenes silylcyanation 1073 – mechanistic interpretation, roles 976 sinapyl alcohol 1630 stoichiometric and catalytic version of directed single-site catalysts 1069 dihydroxylation 1512 single-stage process 498 stoichiometric oxidants 1486 in situ polymerization 221 stoichiometric reaction 491 slurry phase hydrogenation 1045 strain-promoted azide-alkyne click reaction sodium dodecyl sulfate (SDS) 855, 1298, 1497, (SPAAC) 1551 1664 Strecker method 904 sodium thiophene-2-carboxylate 739 Streptomyces lividans 851 sole energy source 1656 styrene 192, 194, 202, 427, 731 sol–gel process 1000, 1077 – asymmetric hydroformylation 59 solid material 999 – formation 964 – catalysts 1136 – hydrogenation 1244, 1279 – surface properties 999, 1031 – stereospecific polymerization 200 soluble organometallic catalysts 1499 – syndiospecific polymerization 243 solvatophobic effects 846 – yield 1017 solvent-free reaction 823 substituted (hetero)arenes, synthesis of 411 Sonogashira coupling 431, 819, 1121, 1122, substituted cycloalkanones 1342 – kinetic resolution 1469, 1477, 1489, 1494 – in air under amine-free conditions 819 substituted tetrahydrofuran synthesis 1206 – catalytic generation of alkynones and sugars alkenones 1464, 1474 – conversions of 1619–1621 – cross-coupling reaction 431, 432 sulfates 1583 Sonogashira reactions N-sulfinyl-based chiral sulfur-alkene – decarboxylative and non- ligands 1566 decarboxylative 538 sulfonamide-amide 637 southern pine beetle 1110 sulfonated ligands 36 space-time yield (STY) 1501 sulfonated phosphine ligand (TPPTS) 31 spectroscopic techniques 1080 sulfoxantphos (SX) 870, 1021, 1022 spiroketal structures 174 sulfur 1557, 1569 square-planar configuration 129 – bridged bis(phenolato)-ligands 194 stacked membrane reactor design 1046 – carbonylation reactions 1560 π–π staking interactions 1187 – hydrogenation/isomerization 1563 stannylation reactions 892 – push effect 1567 stereoblock – thiacrowns, catalytic synthesis 1568 Index 1731 sunflower oil 1581, 1582 t superabsorbent polymers 1610 TACN ligands 711 supercritical CO2 1050, 1343 tactic homopolymers 218 supercritical fluids 1000 tandem catalysis processes 227 supported aqueous phase 1020 tandem hydroformylation/indole Fischer supported hybrid ionic liquid (SMNP) synthesis 1201 materials 1057 tantalum hydride 1313 supported ionic liquid phase 1030 tautomerization 1323 supported liquid phase (SLP) catalysis 1002 tazarotene 431 – catalytic performance of 1010 telomerization 343, 372, 1583, 1594 – hydroformylation plant, flow-scheme 1012 – of 1,3-butadiene 343, 350, 361, 362 supramolecular – with formic acid 374 – catalysts 857 temperature stability 226, 247 – ligands 847, 1077 – Ni(II) catalysts 241 – photocatalysts 1664 terbinafin 431 surface coating 1000 terephthalic acid 465, 483 surface hydrogen 1070 – production 1624 surface organometallic chemistry 1000, 1079 terminal olefins surface organometallic complexes 1076 – hydroformylation 92, 1201 surfactants 1582, 1583 β-terminal selectivity 973 Suzuki–Miyaura coupling reactions 412, 420, terpenes 1581 421, 422, 426, 822, 890, 897, 1094, 1566 terphenyl-substituted diimines 241 – aryl halides 541 tert-butyl hydroperoxide (TBHP) 467, 504, – carboxylic anhydrides 532 549, 851, 1443 switchable catalysis 877, 882 tertiary phosphines 955 – photochemical switching of 885 tethered bis(ureate) zirconium complex 1395 – pressure switching 885 tetraamido macrocyclic ligands (TAML) 712 – self-separating catalyst 881 tetra-anionic tetradentate amidate – solubility with acid–base chemistry 887 ligands 1145 – solvent switchable catalysts 883 tetraarylporphyrinatoiron(III) chlorides 716 symmetrical dialkyl alkynes, tetrabutylammonium borohydride 177 hydroformylation 58 tetrabutylammonium bromide 820 symmetric phenanthrolines 1269 tetrabutylammonium iodide (Bu4NI) syn-acetoxypalladation 507 catalyst 1442 syn–anti isomerization 357 tetrafluoroborato Pd(II)-η2-η3-octadienyl syndioselective polymerization 199 analog 370 syndiotactic copolymers 164 tetrahedral intermediate 1279 syndiotacticity 201 tetrahydroazulene derivative 1103 syndiotactic 1,2 polybutadiene 251, 255 tetrahydroisoquinolines 1470 syndiotactic polyketone 175 tetraimine macrocyclic cobalt complexes 1157 syndiotactic polypropylene 194, 196, 212 tetrakis(pentafluorophenyl)borate 211 syndiotactic polystyrene (sPS) 200, 202, 242, tetrakis(triphenylphosphine)platinum 529 244 tetrametallic complex 854 Synechococcus leopoliensis 1677 2,3,5,6-tetramethylbenzoic acid 1273 Synechococcus lividus 1677 tetramethylcyclopentadienyl 227 syn-selectivity 1511 tetramethyldivinyldisiloxane (dvds) 359 synthesis gas (syngas) 40, 94 N,N,N´,N´-tetramethylethylenediamine – Fischer–Tropsch conversion 347 (TMEDA) 1413 – hydroformylation 40 1,1,3,3-tetramethylguanidinium lactate synthetic Fe2S2 mimics 1151 (TMGL) 1032 synthetic mesoporous Mg 1503 2,2,6,6-tetramethylpiperidine-oxyl syringyl alcohol (TEMPO) 717, 1550 – with O2 catalyzed 544 tetranuclear catalyst 711 1732 Index

tetraphos 121, 124 tosylate 1399 tetrapropylammonium perruthenate – Pd-catalyzed amidation 441 (TRAP) 1517 TPP. see triphenylphosphine (TPP) [tetra(p-sulfonato)]-(tetra-n-butoxy)-calix[4] transamidation 1433–1437 arene 855 transaminases 920 tetrapyridyl-uniamine cobalt(III) α-transaminases (TAs) 920 complex 1169 transamination 1088 tetrasubstituted olefins transesterification 277, 1583, 1593 – hydrogenation 628, 629 transfer hydrogenation 1,3,4,5-tetrasubstituted pyrazoles – catalyst 1442 – one-pot four-step synthesis 1475 – non-classical iron trihydride complex TFSA. see trifluorosulfonic acid (TFSA) 730 theaflavin–model, for tea stains 520 transformation 1521, 1525, 1583, 1584 thermal cracking 1262 transition metal 213 thermal thiol-ene reaction 1550 – catalysis 238, 758, 1196, 1372, 1463 thermodynamically-controlled approach 913 –– in BV reaction 1487 thermodynamic endo-cyclization 1414 – complexes 233, 1031, 1337, 1525 thermomorphic strategy 879 – insertion polymerization 242 thermoplastic material 200 – ketimide complexes 231 thermoregulated catalysis 881 – pincer complexes 889–896 thietane transition-metal elements 1307 – rhenium-catalyzed trimerization 1569 transition metal polypyridine catalysts 1167 thin film coating materials 1003 transition state 1528 thioanisoles – ligand-free 966 – derivatives 1123 – proposed stereo-model 1388 – sulfoxidation of 850 transmetalating agent 1209 thioethers 1341 transmission electron microscopy (TEM) thiolato-bridged dirhodium complexes 1559 223 thiophene derivatives 739 transoid butadiene molecules 371 thiophosphine ligands 1561 trans-1,4 polybutadiene 254 thymine 1-acetate (THA) 719 trans-1,4-polyisoprene 771

TiO2 nanoparticles trans-spanning ligands 835 – H2-evolving rate of 1678 transvinylation 507 titanium 204, 235 trialkylaluminium 208 – carbon bond 207 trialkylamines 1314 – catalysts 192, 251, 252, 1293, 1294 trialkylphosphine ligand 451 2 – complexes 194, 200, 210, 242, 336 trialkylsilyl isonitriles (R 3SiNC) 1294 – Ti-C σ bonds 1294 1,2,4-triazoles 1469 – Ti-C bond strengths 1309 1,2,4-triazolyl carbenes 1545 – Ti(III) compounds 201, 243 tributylphosphine sulfide 1288 – Ti(IV) catalyst precursors 201, 243 1,3,5-tricarboxybenzene 474 i – Ti(IV) isopropoxide (Ti(O Pr)4), 1427 tri-coordinated insertion complex 968 titanium dioxide supported gold catalyst tricyclic enones 1287

(Au/TiO2) 1446 tricyclic intermediate 1105 titanocene 252 tricyclodecanedialdehyde (TCD- – catalyzed addition, of amines to alkynes dialdehyde) 50 1390 tricyclopentadiene 1349 Tolman electronic parameter (TEP) 352, 809, tridentate ligands 638, 708 836 tridentate pyridinediimine ligand 721 toluene 483 triesters 118 toluene diisocyanate 1261 triethanolamine (TEOA) 1668 Topas cycloolefin copolymers 245 triethoxy-silane 1002, 1592 tosylamides 1415 triethylaluminium (TEA) 325 Index 1733

triflate (OTf ) 1399 trivalent phosphorus compounds 829, 842 trifluoroacetate (Tfa ) 1399 trivalent phosphorus protection 844 trifluoroacetic acid 727, 729 TS. see transition state (TS) trifluoromethylated indole 757 TsOH, bulk electrolysis 1157 trifluoromethylations 1120 Tsuji-Trost reaction 1565 trifluoromethylbenzylboronic acid 1430 TTBMPP. see tris(2-tert-butyl-4- trifluoromethyl nucleophiles 537 methylphenyl)phosphite (TTBMPP) trifluorosulfonic acid (TFSA) 1275 tungsten 1338 triglycerides 1582 – carbene 1105 – common fatty acid residues 1637 – catalysts 1339 β-triketimine cobalt complexes 268 – hexacarbonyl 1103, 1104, 1105 trimer (2,4-dimethyl-1-heptene) 214 – hydrides 1071, 1072 trimeric iron hydride [HFe3(CO)11] turnover frequency (TOF) 622, 763, 1137 1663 turnover number (TON) 622, 647, 763, 821, trimerization reaction 340 1137 2,2,2-trimethylacetamide 1433 two-component ring expansion reaction 1200 trimethylaluminium 207 L-tyrosine 904 trimethylamine N-oxide 728 2,4,5-trimethylbenzaldehyde 486 u trimethyl-1,4-benzoquinone (TMBQ) 544 Ugi reaction 1195 trimethylphenol (TMP) 544 Ullmann coupling reaction 437, 455 trimethyl phosphite 844 Ullmann–Goldberg cross-coupling 2,3,6-trimethylquinone 716 reactions 754 1,4,7-trimethyl-1,4,7-triazacyclononane ultrahigh molecular weight polyethylene 521 (UHMWPE) 237 N,N´,N´´-trimethyl-1,3,7- unactivated methyl esters triazacyclononane 1520 – hydrogenation of 1644 triphenylphosphine (TPP) 57, 350, 356, 731, un-protected indole 755, 1011, 1638 – aminocarbonylation 1452 – concentration 1086 α,β-unsaturated acid derivatives – derivatives 373, 1010 – Rh catalyzed hydrogenation of 635 triphenylphosphine trisulfonate (TPPTS) 71, α,β-unsaturated aldehydes 45, 48, 1298 1595 γ-unsaturated carbonyl compound 1102 triphosphine borane 721 α,β-unsaturated carboxylates 1510 TriPhosPh ligand 646 α,β-unsaturated esters 639 TriPhosPh ruthenium complexes 651 unsaturated fatty acid tripropylene 26 – double bond modifications 1639 tris[3,5-bis(trifluoromethyl)phenyl]phosphine – modifications of the double bonds 1638

(P[C6H3(CF3)2]3) 1663 – selective Fe catalyzed oxidative cleavage to tris(carboxyethyl)phosphine 1546 aldehydes 1645 tris(β-diketonato)vanadium complexes 195 ω-unsaturated fatty acid tris(2,4-di-tert-butylphenyl)phosphite 44 – hydrocyanation 1640 tris(m-sulfophenyl)phosphane (TPPTS) unsaturated fatty acid methyl ester (FAME) 1560 – isomerizing methoxycarbonylation 1640 tris(N-pyrrolyl)phosphine (P(Pyr)3) 1659 α,β-unsaturated β-iminoamines preparation tris-o-tolylphosphine 373 – titanium-catalyzed three-component tris(2-tert-butyl-4-methylphenyl)phosphite route 1214 (TTBMPP) 1638 unsaturated ketone 1092 trisubstituted pyridines 1479 α,β-unsaturated ketones 730, 739, 1467 trisubstituted triazoles – cycloaddition of 1116 – four-component synthesis 1215, 1548 β-unsaturated ketones 851 Triton X-100 855 unsaturated lactam Triton-X305 1018 – diastereoselective hydroformylation 63 1734 Index

α,β-unsaturated nitriles vitamin B12a 1109 – hydroformylation 1197 vitreous carbon sponge (VCS) 1141 0 unsaturated Pd L2 type complexes 955 vulcanization 251 unsymmetrical bidentate ligands 163 unsymmetric alkynes w – hydroamination of 1391 Wacker oxidation 98, 415, 490, 502, 1645 unsymmetric phenanthrolines 1269 – PdCl2/dimethylacetamide catalyzed 1645 UpJohn conditions 1511 – of terminal alkenes 505

urea-H2O2 adduct 1490 Wacker product 497 ureas Wacker-type reactions 506, 507 – selenium catalyst, use of 1279 water – adsorption capacity 1051 v – concentration in acetic acid 476 valence electron number 197 – diiron-based catalyst systems function 1664 valeraldehyde 46 water-gas shift reaction 98, 1058 γ-valerolactone 1487, 1626 water immiscible solvents 902 valuable rubbers 1349 water mediated pathway 1435 vanadium water-miscible solvents 902 – catalysts 245, 254 water oxidation catalyst (WOC) 1137 – compounds 205, 1000 water (proton) reduction 1656 van der Waals forces 846 water soluble catalysis 1276 vanillin water soluble cobalt diimine-dioxime – production 1634 complexes 1156 varenicline 420 water soluble ionic cobalt porphyrin vaulted BINOL (VANOL) 1489 complexes 1172 vegetable oils 1582 water splitting reaction 1135, 1656 Vemurafenib 426, 431 Weinreb amides 1453 Vibrio fluvialis 921 western pine beetle 1110 vic-diol 1521 WGS activity 1059

vicinal silanols 1070 Wilkinson’s catalyst (RhCl(PPh3)3) 526, vinyl acetate 60 1044 – asymmetric hydroformylation 60 windshield wiper effect 832 vinyl addition homopolymerization 245 Woodward-Hoffmann rules 1106 vinyl arenes – hydroformylation 53 x vinyl bromides xanthenes 362 – first coupling 452 – ring, with sulfur 1674 4-vinylcyclohexene (VCH) 350 xantphos ligand 1440 vinylcyclopropyl derivative 1102 X-ray crystallography 1080 vinyl-1,1-diarenes XylBINAP containing complex 659 – Rh-catalyzed hydroformylation 53, 54 o-xylene 478 vinyl esters – gas phase aerobic oxidation 471 – of long-chain carboxylic acids 506 – liquid-phase oxidation of 479 vinyl ethers 1338 D-xylose vinyl halides 426 – without acetylation 372 vinylic oxidative addition 1310 vinyl monomers 170, 199 y – copolymerization 171 (R,S)-YANPHOS 59 vinyl norbornene yttrium complex 771 – isomerization of 1369 2-vinylpyridine 233 z vinyl terminated polymer chains 227 zeolite 1000 vinyl transfer 134 – catalysts 118 Index 1735

zero-order rate kinetics 1381 zirconium complex [Zr(NMe2)4] 194, 233, zero oxidation states 113 1393, Ziegler catalysts 205, 247, 334 – with phosphinimide ligands 230 Ziegler–Natta catalysis 191, 196, 203, 204, 205, – zirconium(III) complexes 194

217, 218, 225, 232, 248 – zirconium(IV) chloride (ZrCl4) 1427, 1490 – heterogeneous 202 zirconium tert-butoxide 1437 zinc metal 738 zirconocenes 209, 212 zinc porphyrin 1665, 1681 – catalysts 191, 197, 208, 1427 zirconacyclopentenes 1293 Zn/H-Beta 1409 zirconium 209 Zn(II)-porphyrins 859 – alkyl cations 1394 (Z)-selective Ru catalysts – catalysts 195, 210 – application of 1642 – titanium salan and salalen complexes, zwitterionic zirconium complex 1395 structures of 236 Zymomonas mobilis 922