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Organometallic Chemistry of Rhenium Peter Gerald

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Organometallic Chemistry of Rhenium Peter Gerald ORGANOMETALLIC CHEMISTRY OF RHENIUM A thesis submitted by PETER GERALD EDWARDS, B.Sc., A,R,C.S, for the DEGREE OF DOCTOR OF PHILOSOPHY, UNIVERSITY OF LONDON Chemistry Department, Imperial College of Science and Technology, London, SW7 2AY. June, 1979. TABLE OF CONTENTS FAGEf: ACKNOWLEDGEMENTS. 3 ABSTRACT 4 ABBREVIATIONS 6 INTRODUCTION 7 CHAPTER 1 Introduction 9 Results and Discussion CHAPTER 2 Introduction 20 Results and Discussion 21 .CHAPTER 3 Introduction 42 Results and Discussion 43 •EXPERIMENTAL'SECTION 60 CHAPTER ONE 63 CHAPTER TWO 78 CHAPTER THREE 94 REFERENCES 106 3 ACKNOWLEDGEMENTS I would like to express my thanks to Professor Sir Geoffrey Wilkinson for his continuous encouragement and guidance throughout the period this work was undertaken. I would also like to thank my colleagues including Richard Jones, Kostas Mertis, David Cole-Hamilton, Ernesto Carmona and John Malito for their helpful advice and interesting discussions. In particular I am indebted to Dr. Richard Andersen for his encouragement and Drs. Abdul Malik and Mike Hursthouse for their help in solving crystallographic problems. I thank Moira for typing and helping prepare this thesis and Sue Johnson, Colin Robinson and Roger Lincon for technical. help. I would also like to acknowledge the Science Research Council for financial support. 4 ..ABSTRACT The interaction of the triangulo-trirhenium cluster alkyls, Re3Cts(CH2SiMe3)6 and ResMeg, with carboxylic acids, p-diketones and 1,3-diphenyltriazene leads to partial or complete loss of tetramethylsilane or methane from the end alkyl groups, respectively and the formation or Re(III_) complexes that may be either monomeric, i.e., triangulo-trirhenium, Res, or dimeric, in which two such units are.linked together by carboxylate bridges to give Re6 species. Anew cluster benzyl, Re3Cls(CH.2Ph)6, cluster aryls, Re3Ct9(Ar)6j Ar = -Ph, -4Me-Ph, and tertiary phosphine adducts of the corresponding cyclohexyl Re3Cl3(C6H11)6L3, and of the permethyl, Re3Me9L2,3 have been prepared. The reactions of some of these complexes and of the blue trimethylsilylmethyl cluster, Re3Cls(CH2SiMe3)6 with HCl, CO, NO, PR3, 11.2 and various alkylating agents are described. The syntheses and characterisations of some higher cluster alkyl complexes containing 6, 12 and 18 rhenium atoms. are also given. The results of some 1--ray structure determinations are quoted. TO MY WIFE AND PARENTS 6 S ABBREVIATIONS acac acetylacetonate a.m.u. atomic mass units Ar aryl atm atmosphere e.s.r. electron spin resonance F.t. fourier transform g.l.c. gas liquid chromatography i.r. infra red L ligand He methyl n.m.r. nuclear magnetic resonance OAc acetate Ph phenyl ppm parts per million PRg tertiary alkyl or mixed alkyl aryl phosphine P. T.F.E. polytetraflouroethene py pyridine tl half life z THF tetrahydrofuran In some diagrams and schemes the triangulo metal-metal bonded Rea unit Rem! 11Re is represented as a triangle, i.e. (cf. Scheme 3 Page 40). 7 INTRODUCTION In the past there has been extensive chemistry on rhenium organometallic complexes, largely limited to coordination 1'2'3 compounds. Many rhenium alkyls have also been discovered mainly within the last few years and alkyls are known for all the positive oxidation states except 2 and 5, examples are: Re(I) 6 McRe(C0)5,4 Re'(III) Re3Me9,5 Re(IV) Re3R12,5 Re(VI) ReMe6, Re0R4,7 Re(VII) Re02Me3.6 One of the most interesting alkyl systems to have been produced is the triangulo trirhenium(III) group of alkyls5 which, apart from being the first transition metal cluster alkyls and.peralkyls to have been synthesised, the original claim by Druce8 has since been discounted,9 are based on the well characterised and intensively studied Re3X9 Unit. Many 10 such complexes have been structurally characterised, Re3Cl9, 12 Cs3Re3CI12,11 Re3CF9.(IRt2Ph)3j are examples of a few contributing to a wealth of information on triangulotrirhenium(III) systems. 13'14 This has allowed theoretical studies to be performed, as well as synthetic routes to and properties of these compounds to be investigated in detail. This thesis is concerned primarily with investigations into the reactivity of the triangulo trirhenium(III) cluster alkyls, the study of their properties, and alternative syntheses which has increased their availability. The first chapter deals with the .reactions of these alkyls with weak protonic acids, enabling the discovery of a new series of carboxylates containing six rhenium 15,16 atoms. Cluster carboxylates containing three, four,16 and five16 transition metal atoms have been reported, but only dimeric 8 rhenium carboxylates, e.g., Re2(0Ac)4C12 were previously known.17 A hexamer diketonate was also synthesised, the only previously known acetylacetonates are monomeric, e.g., ReCt2 acac(PPh3)2 and dimeric, 18 e.g., t ReX2 (acac)s ] 2, reactions of the Re(III) alkyls are seen to lead to some higher cluster alkyls of rhenium. In particular, the reaction of Re3CI3(CH2SiMe3)6 with hydrogen is of interest. An alkyl hydrido cluster is produced which, as well as being the first of its kind is relevant to the study of mechanisms in homogeneous catalysis. Alkylhydrido complexes are proposed as intermediates in the catalytic hydrogenation of alkenes to alkanes.19 Transition metal cluster complexes are becoming increasingly important in this respect since, they may combine the catalytic abilities of multi-metal centres or bulk metals as heterogeneous catalysts with those of homogeneous catalysts.20 Many cluster systems have been studied in this capacity, 1,22,23,24 but cluster alkyls have received relatively little attention probably because of the low availability of suitable alkyls and the synthetic difficulties in producing new ones. As a result of the enormous volume of information which has been published on carbonyl and other non-alkyl cluster systems, general synthetic routes can be proposed25 and there is no reason to believe that some of these may not be applied to metal alkyl chemistry. In investigating the synthesis of new aryls of the Rea system, a new cluster phenyl was produced. The only 26 previously known rhenium aryls are of the type ReAr3(PR3)n, and 27 Re2Ar6. CRAFTER 1 INTERACTION OF TRIRHENIUM(III) CLUSTER ALKYLS WITH CARBOXYLIC ACIDS;'13-DIKETONES'AN DIPHENYLTRIAZENE I. INTRODUCTION In this chapter are described the reactions of Re3Cl3(CH2Si.Me3)6 and Re3Me9 with weak protonic acids, specifically carboxylic acids, P-diketones, and diphenyltriazene. 'In these reactions partial or complete loss of the terminal alkyl groups,as SiMe4 or CH4,.occurs with_ the formation of new types- of rhenium complexes. With the exception of one p-diketonato-complex, none of the compounds has been obtained as crystals suitable for x-ray diffraction study. The compounds were characterised by spectroscopic and analytical .techni.ques. The reactions of Re3Ct3(CH2SiMe3)6 with carboxylic acids are summarised in Scheme 1, the reactions of the trirhenium(III) alkyls with p--diketones are summarised in Scheme 2. 'Interaction of 11-Trichloro-hexakis(trimethylsilylmethyl)r triangulo-trirhenium(III) with Carboxylic Acids, The addition of acetic acid to a petroleum solution of Re3Ct3(CH2SiMes)6 at ambient temperatures yields a red precipitate. Analytical, molecular weight, and spectroscopic data for the compound indicate that it is [ReCt(CH2SiMe3)(CO2Me)]6 with the structure (A), shown in diagram 1. Thus the i.r. spectrum shows, in addition to CH2SiMe3 absorptions, bands at 1 455 and 1 520 cm' typical for bridged carboxylato.-groups 10 -1 and a band at 352 cm which may be assigned to the Re-Ct stretch of the bridge chlorine of the Re3Ct3 triangular unit. The 1H nmr spectrum of the compounds shows two singlets at S = 1.26 and 0.07 with relative intensities 3 : 11 respectively. The former peak may be assigned to CH3CO2 and the latter to CH2SiMe3 where the methyl and methylene peaks are coincident, as has been observed for other trimethylsilylmethyl complexes.5 On refluxing an acetic acid solution of Re3Ct3(CH2SiMe3)6j a dark green compound is obtained. On the basis of analytical, molecular weight, and spectroscopic data this compound can be formulated as [ReCt(CO2Me)2]6 with structure (B) as shown in diagram 1. In addition to acetato-bands in the i.r. comparable to those of the first compound there are two bands at 1 720 and -1 28 1 627 cm typical for unidentate carboxylato-groups. The 1H nmr spectrum in pyridine shows two singlets of equal intensity at S = 1.24 and 1.95 the former being assigned to the methyl of the bridging, the latter to the unidentate acetate. With trifltioroacetic acid the room-temperature reaction leads to a red, petroleum-soluble compound, [ReCt(CH2SiMe3)(CO2CF3)]6, similar to the acetate. The reaction has been followed by nmr spectroscopy where the liberation of one mole equivalent of tetramethylsilane per rhenium atom can be observed. The i.r. spectrum shows bands due to bidentate carboxylato-groups and, in addition, there is a v(C-F) band at 1 204 cm 1. Several other carboxylic acids were used in order to obtain crystalline complexes, unfortunately unsuccessfully. Other complexes obtained were from acids such as picolinic, nicotinic, phenylacetic, 11 DIAGRAM 1 Me 0 --Cl MesSiCH2 Ct',-_ R 0~ Re Re C Cl l Me=- C '0 Me—C Me Me-~ \ 0 0 Cl---_ --Cl 04b R`R Re 4 Re Me3SiCH2 C. \ =0 Me (A). (B) Me 4 R 04/ R Me Me 0 • Me- - _R Me 0 ~~e 'ittiMe (C) (D) Proposed structures for rhenium cluster carboxylates. In these and other diagrams the ligands around only two rhenium atoms are shown for clarity. Although the planar metal-metal bonded Rea triangular units with their bridging Cl or Me groups are shown eclipsed they may in fact be staggered, i.e., (A) Re6Cl6(CH2SiMe3)6(CO2Me)6, (B) Re6Cl6(CO2Me)12, (C) Re3CI3(CH2SiMe3)3(C5H4NCO2)3, and (D) Re6Me12(CO2Me)6 12 malonic, benzoic, and adamantane-l-carboxylic which react similarly.
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