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Formation of Borane Adducts and Some Complexes Starting from N-Heterocyclic Carbenes

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Formation of Borane Adducts and Some Complexes Starting from N-Heterocyclic Carbenes Formation of Borane Adducts and Some Complexes Starting from N-Heterocyclic Carbenes Doctoral Thesis (Dissertation) to be awarded the degree Doctor rerum naturalium (Dr. rer. nat.) submitted by Ming Liu from Fuyang City Provinz Anhui, V. R. China approved by the Faculty of Natural and Materials Science, Clausthal University of Technology Date of oral examination 10.03 2017 Dean: Prof. Dr. rer. nat. Winfried Daum Chairperson of the Board of Examiners: Prof. Dr. Diethelm Johannsmann Supervising Tutor: apl. Prof. Dr. Andreas Schmidt Reviewer: Prof. Dr. Dieter E. Kaufmann Die vorliegende Arbeit wurde in der Zeit vom Dezember 2012 bis March 2017 unter der Leitung von apl. Prof. Dr. Andreas Schmidt am Institut für Organische Chemie der Technischen Universität Clausthal durchgeführt. Teile dieser Arbeit wurden in folgenden Publikationen veröffentlicht: M. Liu, C. Herzberger, C. F. Otto, T. Freese, J. C. Namyslo, A. Schmidt, Borane adducts of punicine and of (pyridinium-1-tl)-2-and-3-phenolates. (manuscript in preparation) M. Liu, Jan C. Namyslo, Nieger, M., A. Schmidt, From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer. Beilstein J. Org. Chem. 2016, 12, 2673-2681. M. Liu, M. Nieger, E. G. Hübner, A. Schmidt, Formation of N-Heterocyclic Carbenes by Tautomerization of Mesomeric Betaines: Cyclic-boron adducts and palladium complexes from 2-(imidazolium-1-yl)phenolates. Chem. Eur. J. 2016, 22, 5416-5424. (hot paper) M. Liu, M. Nieger, A. Schmidt, Mesomeric betaine – N-heterocyclic carbene interconversions of 1,2,4-triazolium-phenolates. Sulfur, selenium, and borane adduct formation. Chem. Commun. 2015, 51, 477-479. N. Pidlypnyi, S. Wolf, M. Liu, K. Rissanen, M. Nieger, A. Schmidt, N-Heterocyclic carbenes from ylides of indolyl-imidazolium, azaindolyl-imidazolium, and indolyl- triazolium salts, and their borane adducts. Tetrahedron 2014, 70, 8672-8680. Weitere Veröffentlichung: A. Schmidt, M. Liu, Recent advances in the chemistry of acridines. Adv. Heterocycl. Chem. 2015, 115, 288-353. List of Abbreviations abs absolute AcOH acetic acid AH alternant hydrocarbon aNHC abnormal N-heterocyclic carbene 9-BBN 9-borabicyclo[3.3.1]nonane Bn benzyl Bu butyl CCMB cross conjugated mesomeric betaine CD3OD deuterated methanol CMB conjugated mesomeric betaine COD 1,5-cyclooctadiene Dipp 2,6-diisopropylphenyl DMF dimethylformamide DMSO dimethylsulfoxide EI-MS electron impact mass spectrometry Et ethyl GC-MC gas chromatography mass spectrometry HR high resolution Hz Hertz IAd 1,3-di(adamantyl)imidazol-2-ylidene IR infrared J coupling constant m multiplett MB mesomeric betaine Mes mesitylene MS mass spectrometry mp melting point n normal NHC N-heterocyclic Carbene NMR nuclear magnetic resonance h hour PCCMB pseudo-cross-conjugated mesomeric betaine ppm parts per million (NMR spectroscopy) rNHC remote N-heterocyclic carbene t triplet (NMR spectroscopy) tBu tert-butyl THF tetrahydrofuran Table of Contents 1 General introduction ....................................................................................................... 1 1.1 Mesomeric betaines ................................................................................................. 1 1.2 N-heterocyclic carbenes .......................................................................................... 5 1.3 Area of overlap between mesomeric betaines and N-heterocyclic carbenes .......... 7 1.3.1 Interconversions of normal (nNHC) and anionic N-heterocyclic carbenes and mesomeric betaines (CMB) ....................................................................... 7 1.3.2 Interconversions of normal N-heterocyclic carbenes (nNHC) and ylides ....... 9 1.3.3 Interconversions of normal, abnormal, and remote N-heterocyclic carbenes (nNHC, aNHC, rNHC) and cross-conjugated heterocyclic mesomeric betaines (CCMB) ............................................................................................ 10 1.3.4 Interconversions of normal N-heterocyclic carbenes (nNHC) and pseudo-cross-conjugated heterocyclic mesomeric betaines (PCCMB) ......... 11 1.4 Imidazole ............................................................................................................... 12 1.5 1,2,4-Triazole ........................................................................................................ 13 2 Motivation .................................................................................................................... 15 3 Results and discussion .................................................................................................. 16 3.1 Synthesis of 1,2,4-triazolium perchlorates ............................................................ 16 3.1.1 Synthesis of triazolium betaines ..................................................................... 18 3.1.2 Reaction of triazolium salts/betaines with sulfur ........................................... 21 3.1.3 Reaction of betaines with triphenylborane and tris(pentafluorophenyl)- borane ............................................................................................................. 22 3.1.4 Synthesis of 3-phenyl-4H- benzo[e][1,2,4]triazolo[3,4-c][1,4,2]oxazaborininium-4-ide ......................... 24 3.1.5 Synthesis of triazoleselenones ........................................................................ 26 3.2 Synthesis of imidazolium salts and betaines ......................................................... 27 3.2.1 Deprotonation of betaine with base ................................................................ 29 3.2.2 Reaction of betaines with sulfur ..................................................................... 30 3.2.3 Reaction of imidazole betaines with borane compounds ............................... 31 3.2.4 Deprotonation of borane compound 74b with base ....................................... 35 3.2.5 Reaction of imidazole betaines with palladium complexes ........................... 36 3.2.6 Reaction of imidazole betaines with gold complexes .................................... 38 3.2.7 Reaction of imidazole betaines with rhodium complexes .............................. 39 3.2.8 Reaction of imidazole betaines with nickel complexes ................................. 41 4 Summary and conclusion ............................................................................................. 43 5 Experimental section .................................................................................................... 46 5.1 General considerations .......................................................................................... 46 5.2 General procedure for the synthesis of triazolium salts and mesomeric betaines . 47 5.3 General procedure for the synthesis of thiones, selenium and boron adducts ...... 54 5.4 General procedure for the synthesis of imidazolium salts and mesomeric betaines .................................................................................................................. 70 5.5 General procedure for the synthesis of carbenes, thiones and boron-adducts....... 82 5.6 General procedure for the synthesis of complexes ................................................ 97 6 X-ray analysis data ..................................................................................................... 106 6.1 Crystal structure determination of 4-(2-Hydroxy-5-methylphenyl)-1-phenyl-4H- 1,2,4-triazolium perchlorate 59b ......................................................................... 106 6.2 Crystal structure determination of 4-methyl-2-(1-phenyl-4H-1,2,4-triazolium- 4-yl)phenolate hydrate 60b ................................................................................. 110 6.3 Crystal structure determination of (4-methyl-2-(1-phenyl-4H-1,2,4- triazolium-4-yl)phenoxy)-tris-(perfluorophenyl)-borate 62c .............................. 114 6.4 Crystal structure determination of 4,4-di-ethyl-3-phenyl-4H-benzo[e][1,2,4] triazolo[3,4-c]1,4,2]oxaza-borininium-4-ide 63a .............................................. 122 6.5 Crystal structure determination of 1-benzyl-3-(2-hydroxyphenyl)-1,3-dihydro- 2H-imidazole-2-thione 71d ................................................................................. 130 6.6 Crystal structure determination of 3-(but-3-en-1-yl)-4,4-diphenyl-4H- benzo[e]imidazo-[2,1-c][1,4,2]oxazaborininium-4-ide 73c ................................ 136 6.7 Crystal structure determination of 3-benzyl-4,4-diphenyl-4H- benzo[e]imidazo[2,1-c][1,4,2]-oxazaborininium-4-ide 73d ............................... 141 6.8 Crystal structure determination of (2-(3-butyl-1H-imidazolium-1-yl)benzyl)- tris-(perfluorophenyl)borate 74b ......................................................................... 159 6.9 Crystal structure determination of 1-benzyl-3-(2hydroxyphenyl)-1,3-dihydro- 2H-imidazole-2-thione 76d ................................................................................. 169 6.10 Crystal structure determination of mono(bis(3-butyl-1-(2-hydroxyphenyl)-1H- imidazolium-2-yl)gold) monochloride 77 ........................................................... 176 6.11 Crystal structure determination of tris(3-butyl-1-(2-oxidophenyl)-1H- imidazolium-2-yl)rhodium 79 ............................................................................. 179 6.12 Crystal structure determination of bis(3-butyl-1-(2-oxidophenyl)-1H- imidazolium-2-yl)nickel 80 ................................................................................. 189 7 References .................................................................................................................
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