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Signature Redacted - C Department Pf Chem.Istry "The Synthesis and Reactivity of Thiolate Bridged Diiron Hexacarbonyl Complexes" by JEFFREY BARMONT HOKE B.S., The Pennsylvania State University (1983) SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 1987 c Massachusetts Institute of Technology 1987 Signature of Auth@ Signature redacted - C Department pf Chem.istry Certified by Signature redacted $iitmar Seyferth Thesis Supervisor Accepted by Sign ature redacted Glenn'A. Berchtold, Chairman Departmental Committee on Graduate Students MASSACHUSE ITS NS: j7 OF TECHNOLOC3Y LIBRARMES Archives -2- This doctoral thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Alan Davison Signature redacted Chairman Professor Dietmar Seyferth1. Signature redacted Th L&sAs Superviq Professor Richard R. Schrock Signature redacted -3- This Thesis is Dedicated with love to my wife, Elaine, and to my parents -4- "The Synthesis and Reactivity of Thiolate Bridged Diiron Hexacarbonyl Complexes" by Jeffrey Barmont Hoke Submitted to the Department of Chemistry on May 22, 1987 in partial fulfillment of the requirements for the Degree of Doctor of Philosophy ABSTRACT Chapter 1: 2 "Synthesis of (p-RlC=NR )(p-RS)Fe 2 (CO) 6 " New p-iminoacyl complexes of the type (p-RlC=NPh)(p- RS)Fe 2 (CO) 6 were prepared from the reactions of triiron dodecacarbonyl with thioimidates (RlC(SR)=NR2 ). The geome- try of the bridging iminoacyl and thiolate ligands was determined primarily from IR and 1 3 C NMR spectral correlations to related acyl and thioacyl systems. In related work, reaction of [Et 3 NH][(p-CO)(p-RS)Fe 2 (CO) 6 ] with N-phenyl benzimidoyl chloride was found to be an alternate and superior route to complexes of this class. Chapter 2: "Synthesis and Reactivity of (p-a,n-C=CR1 )(p- RS) Fe 2 (CO) 6" New p-acetylide complexes of the type (p-a,n-C=CR1 )(p- RS)Fe 2 (CO) 6 were prepared from the reactions of [Et 3 NH][(p- CO)(p-RS)Fe 2 (CO) 6) with 1-bromoalkynes. Fluxionality of the alkyne derived, bridging acetylide ligands was illustrated in the variable temperature 1 3C NMR study of (p-a,n- C=CSiMe 3 )(P~tBuS)Fe 2 (CO) 6. Subsequent reaction of these acetylide products with diethylamine, aniline, t-butylamine, and triphenylphosphine generated products derived from nucleophilic attack of the base at the s-carbon atom of the brid 7 ing acetylide ligand. In addition, reaction of (p-a,n- C=CR )(p-RS)Fe 2 (CO) 6 with dicobalt octacarbonyl and diiron nonacarbonyl yielded unusual homo- and heterometallic acetylide clusters, four of which have been characterized by X-ray crystallography. Surprisingly, the specific cluster isolated depended not only on the added metal carbonyl the particular (Co2 (CO) 8 vs. Fe 2 (CO) 9 ), but also on substituent (R1) in (p-a,n-C=CR1)(u-RS)Fe2 (CO) 6 - -5- Chapter 3: "Reactions of [Et 3 NH][(p-CO)(p-RS)Fe 2 (CO) 6 ] with Acetylenes and a,O-Unsaturated Acid Chlorides" Reaction of [Et 3 NH][( -CO)(p-RS)Fe 2 (CO) 6 ] with alkyl and aryl acetylenes (RlC=CR ) produced neutral p-vinyl com- 2 plexes of the type (p-a,n-R'C=CHR )(p-RS)Fe 2 (CO) 6 - Presum- ably, formation of these products resulted from the in-situ protonation of an intermediate vinylic anion by the tri- ethylammonium cation. 1 H NMR correlations have shown that overall addition of the diiron and proton units has occurred in a cis fashion. In some cases, reaction of [Et 3 NH][(p- CO)(p-RS)Fe 2 (CO) 6 ] with acetylenes generated the a,0- unsaturated acyl complexes 2 (p-RlC(=CHR )C=O)(p-RS)Fe 2 (CO) 6 as well. Formation of these acyl products resulted not only from protonation by the triethylammonium cation, but also from insertion of carbon monoxide into an iron-vinyl a-bond. Bridging acyl complexes of this general class were prepared directly from the reactions of x,o-unsaturated acid 1 2 chlorides (R (R )C=CHC(O)Cl) with [Et 3 NH][(p-CO)(p-RS)- Fe 2 (CO)6 ]. In refluxing THF, these vinylacyl complexes were decarbonylated to the respective p-vinyl derivatives. Chapter 4: "Reactions of [Li][(p-CO)(p-RS)Fe 2 (CO) 6 ] with Acetylenes" Unexpectedly, reaction of acetylenes (RlC=CR 2 ) with [Li][(p-CO)(p-RS)Fe 2 (CO) 6] followed by reaction of the anionic intermediate with an electrophile generated products derived from complex intramolecular rearrangement chemistry involving vinyl, carbonyl, and thiolate ligands. In the abscence of the in-situ triethylammonium proton source, unusual vinyl complexes which have incorporated a carbonyl ligand into the organic framework (and in some cases, with concurrent involvement by the thiolate ligand) were prepared and characterized by X-ray crystallography. Unexpectedly, the specific type of product obtained depended on the organic group of the RS ligand, the substituents on the acetylene, the reaction temperature, and the added electrophile. Of particular interest was the crystal structure of a novel, delocalized vinylcarbene complex. 2 Chapter 5: "Synthesis of (p 3 ,0 -C=CHR)(p-CO)Fe 3 (CO) 9 " 2 Trinuclear vinylidene complexes of the type (p 3 ,n - C=CHR)(p-CO)Fe 3jCO) 9 were prepared from the reactions of 1- bromoalkynes (R C=CBr) with [Et 3 NH][HFe 3 (CO) 1 1 ]. Structure assignment by the standard analytical and spectroscopic techniques was confirmed by X-ray crystallography. Presu- mably, formation of these products resulted from an intramo- lecular hydride migration to an initially formed acetylide intermediate. Thesis Supervisor: Dr. Dietmar Seyferth (Prof. of Chemistry) -6- TABLE OF CONTENTS Page ABSTRACT .. ............................................ 4 "Synthesis 2 Chapter 1: of (p-R'C=NR )(p-RS)Fe 2 (CO)6" INTRODUCTION ............... 14 RESULTS AND DISCUSSION ..... 17 EXPERIMENTAL General Comments ....... 24 Characterizing Data for EtC(SMe )=Nph................ 25 Characterizing Data for MeC(SMe )=NPh............... 26 Characterizing Data for PhC(SMe )=NPh............... 26 Characterizing Data for MeC(SEt )=NPh............... 27 Synthesis of (p-PhC=NPh)(p-MeS) Fe 2 (CO) 6.. .. .. ..... 28 Synthesis of p-MeC=NPh) (p-MeS) Fe 2 (CO) 6............ 29 Synthesis 30 of (p-EtC=NPh)(p-MeS)Fe2 (CO)6 Synthesis 32 of (p-MeC=NPh)(p-EtS)Fe2 (CO) 6 Preparation 33 of [Li][(p-CO)(p-MeS)Fe 2 (CO)61 - - Reaction with N- of [Li][(p-CO)(p-MeS)Fe 2 (CO) 6 ] Phenyl Benzimidoyl Chloride ............ 33 .. Preparation of 34 [Et 3 NH][(p-CO)(p-tBuS)Fe 2 (CO) 6 Synthesis 34 of (p-PhC=NPh)(p-tBuS)Fe2 (CO) 6 REFERENCES ................................. 36 Chapter 2: "Synthesis and Reactivity of (p-a,n-C=CRl)- (p-RS)Fe 2 (CO) 6 " INTRODUCTION .......................................... 40 RESULTS AND DISCUSSION ................................ 42 -7- EXPER TMENTAL General Comments .................................. 70 X-ray Crystallography ............................. 71 Standard in-situ Preparation of [Et 3 NH][(p-CO)(p- RS)Fe 2 (CO) 6 ] ...................................... 75 Synthesis of (p-a,n-C=CPh)(p-tBuS)Fe 2 (CO) 6 . ....... 75 Synthesis of n-C=CtBu)(p-tBuS)Fe 76 (p-a, 2 (CO)6 Synthesis of (p-a, n-C=CSiMe 3 )(P~tBuS) Fe2(CO ) 6...... 78 Synthesis of (p-a,n-C=CPh)(p-EtS)Fe2 (CO) 6 ... ...... 79 Synthesis of (p-a,n-C=CtBu)(p-EtS)Fe2 (CO) 6 . .. 80 Synthesis of (p-a,n-C=CtBu)(p-PhS)Fe2 (CO) 6 ........ 82 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with Diethylamine ...................................... 83 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with Aniline ........................................... 85 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with t- Butylamine ........................................ 86 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with Triphenylphosphine ................................ 88 Decarbonylation 90 of (p-Ph 3PC=CPh)(p-tBuS)Fe 2 (CO) 6 Reaction of (p-a,n-C=CSiMe3 )(PtBuS)Fe 2 (CO) 6 with Dicobalt Octacarbonyl ............................. 90 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with Dicobalt Octacarbonyl ............................. 91 Reaction of (p-a,n-C=CtBu)(p-tBuS)Fe2 (CO) 6 with Dicobalt Octacarbonyl ............................. 92 Reaction of (p-a,n-C=CPh)(p-tBuS)Fe2 (CO) 6 with Diiron Nonacarbonyl ............................... 94 Reaction of (p-a,n-C=CtBu)(p-tBuS)Fe 2 (CO) 6 with Diiron Nonacarbonyl ............................... 95 Attempted Reaction between (p-a,n-C=CSiMe 3 )(p- tBuS)Fe 2 (CO) 6 and Diiron Nonacarbonyl ............. 97 REFERENCES ............................................ 98 -8- Chapter 3: "Reactions of [Et NH] 3 [(p-CO)(p-RS)Fe 2 (CO) 6] with Acetylenes and M,3-Unsaturated Acid Chlorides" INTRODUCTION .................... 103 RESULTS AND DISCUSSION .......... 104 EXPERIMENTAL General Comments ............ ......... 124 Standard in-situ Preparation of [Et3NHI[ (p-CO) (p- RS)Fe 2 (CO) 6 ]. ................ 125 Synthesis of (p-a,n-EtOC=CH 2 )(PtBuS)Fe 2 (CO) 6 ... .. 126 Synthesis of (p-a,n-MeO CC=CHCO 2 2 Me)(p-tBuS)Fe 2 (CO)6 127 Synthesis of (p-a,n-MeC=CHCO 2 Me)(p-tBuS)Fe 2 (CO)6 128 Synthesis of (p-a,n-HC=CHCO 129 2 Me)(p-tBuS)Fe 2 (CO) 6 Synthesis of (p-a,n-HC=CHC(O)Me)(p-tBuS)Fe 131 2 (CO) 6 Synthesis of (p-a,n-PhC=CHPh)(p-tBuS)Fe 2 (CO) 6 ..... 132 Synthesis of (p-a,n-HC=CH 2 )(PtBuS)Fe 2 (CO) 6 ....... 133 Synthesis of (p-a,n-PhC=CH 2 )(PtBuS)Fe 2 (CO) 6 and (p-a, n-HC=CHPh) (p- tBuS)Fe 134 2 (CO) 6. ... .. ..- . .. .. .. Synthesis of (p-a,n-Me 3 SiC=CH 2 )(pJtBuS)Fe 2 (CO) 6 and (p-a,n-HC=CHSiMe 136 3 ) (PtBuS)Fe 2 (CO) 6.
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