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Sep 14 1984 Librae S -2 SYNTHESIS AND REACTIVITY OF ORGANOSULFUR IRON COMPLEXES by Gary Bernard Womack B.S., University of North Carolina Greensboro, North Carolina Submitted to the Department of Chemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY September 1984 Massachusetts Institute of Technology 1984 I- -,\ Signature of Author Department of Chemistry Certified by Thesis Supervisor Accepted by Dietmar Se4ferth, Chairman, Departmental Committee on Graduate Students OF TECHNOLOGY SEP 14 1984 LIBRAE S -2- This doctoral thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Richard R. Schrock , Chairman Professor Dietmar Seyferth 4- hesis Sdpervisor Professor Alan Davison V- W- - ,FV W, - & -- , V -3- This Thesis is Dedicated with Love to my wife, Cathie, and to my Parents. -4- SYNTHESIS AND REACTIVITY OF ORGANOSULFUR IRON COMPLEXES by Gary Bernard Womack Submitted to the Department of Chemistry in September 1984 in partial fulfillment of the requirements for the degree of Doctor of Philosphy. ABSTRACT Chapter 1. "Addition of Alkynyllithium Reagents to (p-Dithio)- bis(tricarbonyliron)" Alkynyllithium reagents attack (,p-S )Fe (CO)6 at the sul- fur-sulfur bond cleaving it to form (_P-R6ECS (1-LiS)Fe2 (CO)6 ' Alkylation and acylation of this anion occurs at sulfur to form the (p-RC-ECS) (p-RS)Feg(CO) 6 type complexes. However, protona- tion or metallation with the Group IVA trialkyl- or triaryl- metal halides yields dithiolene complexes. The formation of these products has been explained in terms of an equilibrium between the sulfur-centered anion species and carbanion species resulting from intramolecular thiolate addition to the a and/or carbon atom of the RCEC- group. Thus aldehydes where found to react forming dithiolene complexes by addition of the carbon- ion intermediates to the carbonyl function. Reaction between the PhC=CLi/(p-S 2 )Fe2 (CO)6 system and methylmercuric chloride gave both the sulfur- and carbon-metallated products depending on the reaction conditions. Chapter 2. "The Reactivity of (Di-y-thiol)bis(tricarbonyliron) Toward Electrophilic Alkenes and Alkynes" The piperidine induced additions of the thiol functions of (p-HS) 2Fe 2 (CO)6 to various electrophilic alkenes and alkynes has been studied. With olefins conjugated to a carbonyl group inwhich there is only one alkyl substituent on the s-carbon, Micheal type additions of the thiol ligands to the C=C bands occur to form 2:1 adducts. If two alkyl substituents are attach- ed to the s-carbon, a 1:1 adduct can be isolated inwhich addition to both the C=C and C=O bond has occurred. These products contain -5- a three-carbon bridge between the two sulfur atoms and a hemi- thioketal function. Two consecutive thiol additions to electro- philic acetylenes was found to yield complexes with one- or two-carbon bridges betwen the two sulfur atoms. NMR data was used to determine the type of addition adduct formed as well as an X-ray diffraction study of a one-carbon bridged product. Chapter 3. "Diiron Hexacarbonyl Complexes of Thioesters and Dithioesters" The deprotonation of (P-H2CS2 )Fe2 (CO)6 with lithium diiso- propylamide at -78 0 C in THF generates an organolithium reagent which undergoes intramolecular nucleophilic attack at iron with concomitant Fe-S bond heterolysis. The sulfur-centered anion species thus generated can be trapped with alkyl halides. An X-ray diffraction study of the 1-bromo-2-propanone derived product reveals these compounds are best regarded as coordinated dithio- formic acid ester complexes. Thus an alternate synthesis of these complexes was developed by reacting in-situ generated alkyl dithioformate esters with Fe2 (CO)9 . The formate proton of these ligands can also be removed with LDA resulting in attack of the carbanion at iron. The alkylation of such anionic intermediates allows the isolation of products with an Fe 2 SC tetrahedral core and an exocluster sulfonium function. The X-ray diffraction study of one such product has been completed and reveals a thiocarbonyl unit bridging the two iron atoms per- pendicular to the iron-iron bond. O-Ethyl thioesters react with Fe2 (CO)9 forming products inwhich the ester is bound to an Fe2 (CO)6 unit in the same man- ner as the alkyl dithioformate ligands. However, 0-ethyl thio- formate reacts with Fe2 (CO)9 to give a product of the type [HC(S)OEt]Fe 2 (CO) 6 inwhich the ethoxy oxygen atom is not coor- dinated to the metals. An X-ray diffraction study of this mate- rial revealed no metal-metal bond and that the two Fe(CO)3 units are bridged by the thiocarbonyl groups of the esters. The S-alkyl thioesters were discovered to react with Fe2 (CO)9 or Fe3 (CO)12 to yield diiron hexacarbonyl complexes with both a bridging acyI ligand and bridging thiolate ligand. Chapter 4. "Reaction Between Triiron Dodecacarbonyl, Alkane- thiols and Triethylamine: A New Route to Alkane- thiolate Bridged Diiron Hexacarbonyl Complexes" It has been found that alkanethiolates will react with Fe (CO), in THF to generate a dinuclear anion, [(p-RS) (i-CO)- Fe2(CO), ~ {M]+ (M = Li, Na, Et3NH). This anionic species will react with a variety of electrophiles with loss of a CO ligand to produce (p-RS) (p-E)Fe2 (CO) complexes (E = acyl, Ph2 P, allyl and allenyl). X-ray diffraction studies have been completed for an allyl and allenyl compound. The allyl ligand is bound as a triatomic bridge between the two iron atoms. The allenyl ligand -6- bridges the metals with two carbons in the fashion of a a,'r-vinyl ligand. The dynamic behavior of the p-allenyl complexes was studied by means of variable temperature 1H NMR spectroscopy. + Carbon disulfide reacts with [(li-EtS) (-p-CO)Fe 2 (CO)6] [Et3NH] and in the presence of alkyl halides (p,n2-RS-C=S) (p-EtS)Fe2 (CO)6 type complexes are formed. Methyl isothiocyanate and methyl iso- cyanate react with the same anionic species with protonation of the addition adduct by the ammonium cation to form products contain- ing pi,n2-thiocarbamoyl and yi,n 2 -carbamoyl ligands. Addition of an iron-proton unit across CC bond can also occur to form (p-vinyl) (p-R )Fe (CO)6 compounds. It has also been discovered that the (p,r p-RCO) (P-EtS)Fe 2 (CO) 6 (R = Me, Ph) complexes will 0 react with two equivalents of LiBEt 3H at -78 C to generate RCH 20Li and [(p-EtS)Fe 2 (CO)6 ]~[Li]+. The reactions of this anion with allyl chloride, propargyl bromide and diphenylchlorophosphine were found to proceed analogous to those of the diiron heptacar- bonyl anion. -7- TABLE OF CONTENTS Page ABSTRACT .............. .................................. 4 Chapter 1. Addition of Alkynyllithium Reagents to (p-Dithio)bis(tricarbonyliron). INTRODUCTION ......................... 18 RESULTS AND DISCUSSION .ooo............................... 23 EXPERIMENTAL SECTION ....................................54 General Comments ................................... 54 Reaction Between (p-Dithio)bis(tricarbonyliron), Cyclopentylmagnesium Bromide and Iodomethane .. 55 Isobutylmagnesium Bromide and Iodomethane ...... 56 Cyclopropylmagnesium Bromide and Iodomethane .. 58 Neopentylmagnesium Chloride and Iodomethane ... 59 para-Tolylmagnesium Bromide and Iodomethane ... 60 Isobutenylmagnesium Bromide and Iodomethane ... 62 Reaction Between (p-Dithio)bis(tricarbonyliron), 1-Lithio-l-hexyne and Iodomethane ............. 63 Lithium Phenylacetylide and Iodomethane ........ 65 Lithium Phenylacetylide and Iodoethane ........ 66 Lithium Phenylacetylide and Benzyl Chloride ... 67 Lithium Phenylacetylide and l-Bromo-2-pro panone ................................. ....... 68 4-Lithio-2-methyl-l-buten-3-yne and Iodo- methane .. ..................................... 69 l-Lithio-l-heptyne and Iodomethane ............ 71 1-Lithio-l-heptyne and l-Bromo-2-propanone .... 72 -8- Lithium (Trimethylsilyl)acetylide and Iodo- methane .......................................... 73 Lithium (Trimethylsilyl)acetylide and Iodo- ethane ........................................ 74 Ethynylmagnesium Bromide and Iodomethane ...... 75 Lithium Phenylacetylide and Acetyl Chloride ... 77 Lithium Phenylacetylide and Pivaloyl Chloride 78 Reaction Between (p-Dithio)bis(tricarbonyliron), Lithium Phenyacetylide and Iodonethane After Warming for 30 min .......... 79 Acetyl Chloride After Warming for 30 min ...... 80 Iodomethane After Warming for 1.5 h ........... 80 Reaction Between (yp-Dithio)bis(tricarbonyliron), Lithium Phenylacetylide and Trifluoroacetic Acid .............. ............................ 81 4-lithio-2-methyl-l-buten-3-yne and Trifluoro- acetic Acid .... ................................. 82 1-Lithio-l-hexyne and Trifluoroacetic Acid .... 84 l-Lithio-l-heptyne and Trifluoroacetic Acid ... 85 1-Lithiopropyne and Trifluoroacetic Acid ..... 86 Ethynylmagnesium Bromide and Trifluoroacetic Acid ............................................. 88 Lithium (Trimethylsilyl)acetylide and Tri- fluoroacetic Acid ............................... 89 Methyl 3-Lithiopropiolate and Trifluoroacetic Acid .......... ................................ 91 -9- Reaction Between (i-Dithio)bis(tricarbonyliron), Lithium Phenylacetylide and Trimethylchlorosilane .......................... 92 Trimethyltin Bromide .......................... 94 Triphenylgermanium Bromide .................... 95 Triphenyltin Chloride ........................... 96 Triphenyllead Bromide ......................... 97 Reaction Between (p-Dithio)bis (tricarbonyliron), 1-Lithio-l-hexyne Trimethylchlorosilane ..........................
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