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Mechanism of Hydroformylation of Alkenes

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Mechanism of Hydroformylation of Alkenes MECHANISM OF HYDROFORMYLATION OF ALKENES BY RHODIUM CATALYSTS A Thesis submitted by CHARLES KENNINGTON BROWN, B.A., for the Degree of Doctor of Philosophy of the University of London Royal College of Science Imperial College of Science and Technology London S.W.7. July 1971 2 To my Parents and my Wife 3 ACKNOWLEDGEMENTS I would like to express my gratitude to Professor G. Wilkinson F.R.S. for his encouragement and guidance during the supervision of this work and for his support during the past three years. I would also like to thank all my co-workers during this period, especially Dr G.B. Yagupsky for valuable help and advice, and Mr R. Shadwick and Mr H.J. Smith for technical assistance. I am also indebted to Mrs U.O. Fowler for typing this thesis. 4 CONTENTS Page ABSTRACT b INTRODUCTION 7 CHAPTER I Homogeneous Hydroformylation of Alkenes witn Hydridocarbonyltris(tri- phenylphosphine)rhodium(I) as Catalyst : Low Pressure System. Introduction 17 A. Equilibria 20 B. Rates of Hydroformylation 21 C. Products of Hydroformylation Reactions 31 D. Hydroformylation of Styrene 37 Discuzsion 39 CHAPTER II Hydroformylation at Higher Pressures Introduction 44 A. High Concentration Phospnine Systems 45 B. Relation to other Catalyst Systems 47 Discussion . 48 CHAPTER III Intermediate Species in Hydroformylation; Rhodium and Iridium Analogues Introduction 50 A. Fluoroalkyl Derivatives 52 B. Reactions of1411(C0)(PPh3 )3114 = Rn or Ir, 55 with Ethylene and Carbon Monoxide C. Aryl and Benzoyl Derivatives 66 Discussion 68 CHAPTER IV Interaction of Hydridocarbonyltripftenyl- phosphine Complexes of Rhodium and Iridium with Conjugated Dienes and Allene Introduction 75 5 A. Preparation of the Complexes 75 M(I-A)(C0)(PPn02 , M = Rn, Ir; A = Allylic Group B. Nuclear Magnetic Resonance Spectra 77 C. Reactions with Carbon Monoxide 80 D. Reactions with Hydrogen and Hydrogen 88 Chloride Discussion 90 EXPERIMENTAL 97 REFERENCES 107 ABBREVIATIONS Me methyl Et ethyl i Pr iso-propyl BuBun n-butyl Ph phenyl acac. acetylacetonate Temperatures are given in degrees Centigrade. Pressures are given in the following units 1 atm. = 76 cm Hg = 14.7 lb.in-2. g.l.c. gas-liquid chromatography n.m.r. nuclear magnetic resonance i.r. infra-red i.r. spectra of solids were taken as nujol mulls. 6 ABSTRACT The nydroformylation of alkenes using hydridocarbonyltris(tri- phenylphosphine)rhodium(I), RhH(C0)(PPh3 )3 , under mild conditions 0 (ea 25 and 1 atm.) is described. The dependence of rate, substrate specificity and product distribution on catalyst concentration, partial pressures of carbon monoxide and hydrogen and temperature is discussed in terms of possible mechanisms. The presence of excess triphenylphosphine is important in achieving nigh yields of straight-chain aldehydes from alk-l-enes and the use of molten PPh3 as solvent allows high product specificity to be maintained at higher temperature and pressure (ca 100° and 300-700 lb.in,2). Reactions of RhH(CO) (PPn3 )3 , IrH(C0)(PPh3 )3 and IrR(CO)2(PPh3 )2 with alkenes and CO, H2 or HC1 to give alkyl and acyl species analogous to proposed intermediates in hydroformylation are described. The reactions of these species are shown to be consistent witn the proposed hydroformylation mechanism. In particular the reversible carbonylation and CO-insertion reactions of the rnodium(I) and iridium(I) species and the inhibition of reactions of H2 and HC1 with M(COR)(C0)2(PPh3 )2 , M = Rh, Ir, by CO are noted. The preparation of 11-allylic complexes M(rT-A)(CO)(PPh3 )2 , M = Rh, Ir; A = allylic group, by both diene insertion and Grignard reactions is described. N.m.r. spectra over the temperature range -80° to +80° snow that the allylic groups are "dynamic". The reaction of Ir(r-A)(C0)(PP/13 )2 with CO in solution gives a mixture of)2 0- and)2 r-aliylic species and Ir(0-A) and Ir(COA)(CO) complexes have been isolated. Reactions of these allylic complexes with H2 and HCla're also described. The mechanism of nydroformylation of butadiene is discussed in terms of these results. 7 INTRODUCTION The "Oxon or hydroformylation reaction is tne conversion of an olefin into an aldehyde by interaction with carbon monoxide and , hydrogen in the presence of a catalyst. The reaction was discovered) in 1938 by Roelen during studies on the Fischer-Tropsch process and has acquired considerable industrial importance. It is normally 2 carried out in an inert solvent (often a high-boiling phthalate ester which allows distillation of the reaction products) using a cobalt catalyst and CO + H2 at pressures of 200-300 atm. and temperatures in the range 100-120P. At higher temperatures, 150-180°, reduction of the products to alcohols takes place. These "Oxo-alcohols" are widely used for the production of plasticisers for polyvinylchloride, for the preparation of detergents and as solvents. The annual world capacity3 of Oxo-plant in 1968 was in excess of 1.5 x 106 ton. Much of the early work on the process, recorded in the patent literature, was concerned with industrial and commercial aspects rather than with the reaction mechanism, but after it was realised'. that homo- geneous catalysis was involved mechanisms began to be postulated. -The active catalyst was shown5 to be HCo(C0)4 formed in situ from metallic cobalt, cobalt salts or Co2(C0)8. 6 Alkyl- and acyl-tetracarbonylcobalt(I) complexes were then prepared by reaction of alkyl- and acyl-halides with Na[Co(C0)4 ] and the equili- 6b 7 brium between RCo(C0)4 and RCOCo(CO)3 , (R = alkyl group), demonstrated. The nature and reactions of these alkyl- and acyl-cobalt species has 8 been reviewed. The evidence relating to the mechanism of hydroformylation, which is largely based on the reactions of HCo(C0)4 with olefins at room temperature, has also been thoroughly reviewed9 and a self-consistent scheme which seems to explain the known facts is as follows: 8 Co2 (C0)8+ H2 VI 2HCo(C0)4 (1) • HCo(C0)4 HCo(C0)3 + CO (2) RCH=CH2 RCH=CH2 + HCo(C0)3 (3) HCo(C0)3 RCH=CH2 RCH2CH2Co(CO)3 RCH2CH2Co(C0)4 CO (4) HCo(CO)3 RCHCo(C0), RCHCo(C0)4 CH3 CH3 RICo(C0)4 R,C0Co(C0)3 (5) CO R'COCo(CO)3 RIcoco(c0)4 (6) H2 RICHO + HCo(C0)3 RICOCo(C0)3/- (7) HCo(C0)4 R 'CHO + Co2 (CO)7 H2 MHO + HCo(C0)4 RICOCo(C0)4(HCo(C0)4 (8) )R'CHO + Co2 (C0)8 From equation 5 R' = RCH2 CH2 or RCHCH3 and thus the products from hydroformylation of RCHH2 are the isomeric aldehydes RCH2 CH2 CHO 8 and RCH(CH3 )CHO. Clearly both 4- and 5-coordinate cobalt(I), d , species are important in the mechanism. The straight-chain and branched-chain aldehyde products arising from hydroformylation of alk-l-ene are usually formed in a ratio of < 2:1 and alk-2-ene substrates yield a similar product distribution 10 at low CO pressures because rapid double-bond migration occurs and because terminal double bonds react more rapidly. Higher CO pressures inhibit the isomerisation. Commercial demand for straight-chain products has stimulated much research on modifying the catalytic system to increase the proportion of linear aldehyde and alcohol formed. 9 11 Thus in addition to the use of higher CO pressures it was shown that lower reaction temperatures increase the product ratio. The use of polar solvents, e.g. methylethylketone in hydroformylation 12 of propene, has been claimed to greatly enhance the proportion of linear products. The reaction of HCo(CO)4 with alkenes at 1 atm. and ca room temperature13 gives differing acyl products according to the temperature and composition of the gas phase. These acyls could be collected 14 as stable triphenylphosphine adducts, RCOCo(CO)(PPh3 y ), and the configuration of the acyl group determined by g.l.c. analysis of the methyl esters formed after decomposition of the complexes with 12 and Me0H. This reaction of alkene with HCo(CO)4 under mild conditions 15 was also shown to be affected by the presence of nucleophiles such as benzonitrile. The interconversion of isomeric acyltetracarbonyl- 16 cobalt(I) species was observed at room temperature and, although CO does not alter the final isomer proportions, it slows the reaction which is also very sensitive to solvent. These results were interpreted in terms of the reversible equilibria represented by equations 3, 4 and 5 above and the effect of coordination of solvent or added nucleophile in stabilising tricarbonyl species. It was thus a matter of importance to ascertain wnich of the factors revealed by these low pressure reactions is important in defining reaction products under hydroformylation conditions. These seem to be (i) specificity in direction of addition of Co-H to RCHLICH2 ; (ii) selectivity of reaction of HCo(CO)y between alk-l-ene and alk-2-ene. 10b The rate of alkene isomerisation is known to be dependent on CO pressure 17 and isomerisation of intermediate acyls is thought to be slow compared with the overall process, on the basis of results on the reaction of alkylorthoformates with CO and H2 in the presence of Co2(C0)6 under hydroformylation conditions. This reaction is believed to involve alkyl- and acyl-cobalt intermediates and no isopropyl product was 17 observed from n-propylorthoformate. HC(OR)3 + HCo(CO)4 -0 HCOOR + ROH + RCo(C0)4 RCo(C0)4 + CO -e RCOCo(C0)4 RCOCo(C0)4 + H2 RCHO + HCo(CO)4 RCHO + HC(OR)y -. RCH(OR)2 + HCOOR 10 A small fraction (5%) of n-butyraldehyde was, however, formed from 16 isopropylorthoformate and it has been noted that isomerisation reactions of the acyl species are very solvent dependent, so that it is unlikely that they can be completely excluded under catalytic conditions.
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