South Dakota State University Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange Electronic Theses and Dissertations 1979 Rhodium Complex Catalyzed Alcohol Carbonylation Reactions Joseph Leo Nothnagel Follow this and additional works at: https://openprairie.sdstate.edu/etd Recommended Citation Nothnagel, Joseph Leo, "Rhodium Complex Catalyzed Alcohol Carbonylation Reactions" (1979). Electronic Theses and Dissertations. 5041. https://openprairie.sdstate.edu/etd/5041 This Thesis - Open Access is brought to you for free and open access by Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Open PRAIRIE: Open Public Research Access Institutional Repository and Information Exchange. For more information, please contact [email protected]. RHODIUM COMPLEX CATALY ZED ALCOHOL CARBONYLATION REACTIONS BY JOSEPH LEO NOTHNAGEL A thesis submitted in partical ful fillment of the requir ements for the degree Ma ster of Science , Major in Chemistry , South Dakota State Univers ity "SOUTH DAKOTA STATE UNIVERSITY LIBRARY RHODIUM COMPLEX CATALYZED ALCOHOL CARBONYLATION REACTIONS This dissertation is approved as a creditable and indep endent investigation by a.candidate for the degree , Master of Science, and is acceptable as meeting the dis­ sertation requirements for the degree, but without imply­ ing that the conclusions reached by the candidate are necessarily the conclusions of the major department . Thesis adpiser Date Head , Chemistry Department Date ACKNOWLEDGEMENTS To Dr . Ols·on who, like all great teachers, gave far more than he received; To my wi fe who , as a loving wife, put up with one too many accidents; To my parents , who have always been with me, TABLE OF CONTENTS page . .. , .....•••• ," ......,, . .- •• 1 INTRODUCTION . ,, • • · · .· .· ,,•• · .-. · ., ... .. , , ,. ••• •• HISTORICAL SECTION · • • • • ...· .. • 3 : _. .. : ,· .- .- ,: , , , • .. ' ••••• .. ... .. • EXPERIMENTAL SECTION . I . ... · .. • � : ,· . • • 21 · · · ... .. · Preparat ion of Cuprous Bromide.-, , : ,: �. :. .. 26 · • · . • • • • Preparation of o--Bromochlorooenzene , : • 27 · Drying of Zinc Chlor ide ...... .... .... , ... 29 Preparation of o-Chlorophenyl (d ichloro-.} - phosphine.. ..... ... ....... ........... ..... .. 3 0 Preparation of o�BromophenyL{dichloro}:�· · phosphine .... ............. .............. .. "' . • • 3 1 Preparation of o-Chlorophenyl (dimethyl)� phosphine . • . • . • . • . • • . • . • • • • • • • . 3 1 Preparation of o-Bromophenyl (dimethyl) - phosphine .••......••.•� • • • . • . • • • . • . • • . • • • • • 3 3 Preparation of Dimethylphenylphosphine. ... 33 Preparation of Carbonyl(chloro)bis­ �-chlorophenyl (d imethyl) pho sphine] - rhodium (I) . • • • . • • . • • • . • • • . • . • . • • • • • . • 34 Preparation of Carbonyl (chloro) bis­ J9-bromophenyl(d imethyl) phosphine] - rhodium (I) ••.••••.•••.••.••" . ..... •. • • • . • • . 35 Preparation of Carbonyl (chloro)bis� @ imethylphenylphosphine] - rhodium(I} . • • •• • " . 35 Preparation of Carbonyl(chloro1bis­ £>-chlorophenyl (dimethyl}.phosphine:J -. iridium(rJ.............. ... .. .. .. 36 . • Kinetic Stud ies •..••••.. •. • , ••· . ......�···· 37 page Carbonylation Kinetics. .. .... .. .. .. 3 8 DISCUSSION AND RESULTS, • • , •.••••.• 40 Kinetics ....................." • •••" • , . •. ..... 41 Discussion of Results. for Oxid ative Addition Reaction ....... ... ... .. 43 Discussion of Infrared Spectra .... ... 55 Iridium vs Rhodium Complex . • • • .. • • .. • • t • • • • • 59 Carbonylation Kinetics •••••.••• . .. 59 SUMMARY.. 63 APPENDIX. .. .. ' . .. 65 BIBLIOGRAPHY. - . - . - . - . - . � . 82 LIST OF TABLE page TABLE' I Spectroscopic Data for Listed complexes.·,, 42 TABLE TI Data for Addition of Me! to MCL (CO) (X) 2 in To luene at 220 c..... ... .............. 45 TABLE III Data for Addition of MeI to MC l (CO) (X) 2 in Toluene at 220 C and at Concentration of MeI as Listed. .............. ... ....... 46 TABLE IV Acetolysis rate Ratio for Cis and Trans- 2-Halocyclohexylbrosylates • . •••••.• ••• •••• 4 9 TABLE V Ultraviolet Spectra of the Phosphine P • ••••••••• •••••••• •••••, • • • • • • • • • • Me 2 R • • • 51 TABLE-- VI Ligand Preference Toward Class (a ) or Class (b) Metal Ions. ..... ..... ......... 54 TABLE VII I �co for the Complex Rh Cl (CO) [ Co-xc H }- · 6 4 ( CH ) • . • . • • • • . • • • • . • " • •· • • • • •. • • • • " • 3 2 p J 2 • 5 6 TABLE VIII Data for the Carbonylation of MeOH in Acetophenone at 1650 C in the Presence of Methyl Iodide Promoter, RhCl 3·3 H20 , and the Indicated Phosphine Ligand Added" •· •· ..•, 61 LIST OF FIGURES page , FIGURE' I Kinetic Data for the Oxidative Addition· Reaction Methyl Iodide and the· Listed · ° ..... Metal Complexes at 22 c . ..... , ".,, � , 44 -- FIGURE'· TI Kinetic Data for the Carbonylation Reaction of Methanol in the Presence of Methyl Iodide Promoter and Pho sphine- Metal System Listed at 165° c •••.••••••••• 62 RHODIUM COMPLEX CATALY ZED ALCOHOL CARBONYLATION REACTIONS Abstract Joseph Leo Nothnagel Under the Supervision of Dr . Edwin Olson The oxidative addition reaction of methyl iodide to rhodium or iridium complexes were investigated, incorpor- ating various ortho-substituted dimethylphenylphosphine ligand s· on the metal comp lexes. Evidence of rate enhance- ment for the oxidative addition reaction of the various complexes with methyl iodide wa s found , due to the influ- ence of the ortho� substituents. The complexes studied were: Carbonyl (chloro)bis�(o-chlorophenyl (d imethyl) ­ phoshine]-rhod ium (I) Carbonyl (.chloro)bis-Co-bromophenyl (dimethyl )­ pho sphineJ�rhodiurn(I) Carbonyl (chloro)bis-(d imethylpheny lpho sph ineJ­ rhodium(I } Carbonyl�hloro )bis-Co-chlorophenyl (dimethyl) ­ phosphineJ-iridium (I) The increase in relative reaction rates for the com- · plexes were found to proceed in the order.: Br> Cl ) H for the ortho-phenyl substituent and Ir (Il) Rh(�) for complexes of similiar ligand type . INTRODUCTION Carbonylation of alcohols in the presence of vari ous base metals has been investigated extensively . Reaction over these catalysts is characterized by the use of high 1 temperatures and pres sures . In comparison to the wide spread attention that the base metal catalysts have received , the noble metal catalysts have received very little attention . Mo st recently , investigation of noble metal catalysts have met with .spectacular succ ess . For the carbonylation of methanol , Roth reported a new com- rnercial synthesis of acetic acid using a homogeneous iodide-promoted rhodium catalyst wh ich has such extreme reactiv1ty that it will convert methanol to acetic acid 5 in 99% selectivity at pressures as low as one atmo sphere. None of the various by-products. characteristic of cobalt- cataly�ed reactions were found when using rhodium. The carbonylation is believed to proceed through a series of steps beginning with rapid conversion of methano l to methyl iodide . Methyl iodide then undergoes an oxidative 8 addition reaction with a d square-planar rhodium (! ) comp lex 6 to form a d six-coord inate alkyl rhodium (III) species . Rapid insertion of carbon monoxide into the rhodium-alkyl 2 bond to produce an acylrhodium(I II) complex , followed by reaction of this complex with water to form acetic acid and the original rhodium(!) complex , completes the cylce. The rate-determining step of the carbonylation reaction of methanol with carbon monoxide has been shown to be the oxidative addition of the alkyl halide with the catalyst. The purpose of this project was to investigate the possible rate enhancement , due to anchimeric assistance rendered by the ortho-substituted phenylphosphine ligand directly to the metal center, of the oxidative addition reaction of the alkyl halide with th� catalyst� The substituted groups were; Br , Cl , and H. Also desired was a study of difference in relative reaction rates of iridium complex and a rhodium complex with s1miliar ligand type groups. 3 HISTORICAL SECTION For over forty years, the scientific and industrial communities have been interested in the reaction of 1 carbon monoxide with organic mol�cules. In the reaction, which is known as a carbonylation reaction, carbon monoxide adds to the organic mo lecule in the presence of a catalyst. Carbonlylation reactions lead to a wide variety of products; such as, aldehydes , alcohols, ketones and carboxylic acids . 2 The "Oxo " reaction is the best known carbonylation reaction ._ catalys� . RCH=CH + CO + H RcH cH - H and or _ cH cH 0H 2 2 2 2 8 I � 2 2 Rearrangement of the carbon chain of the starting alkene during "t:he course of the "Oxo " reaction, leads to a variety of isomers of the aldehyde and alcohol as products. Recently, the Monsanto Company has used a carbonylation reaction to produce acetic acid from methanol and carbon monoxid·e. catal st CH - 0H 7000-t0000 psi) 3 � ° 8 2500 - 350 � = - 8 S.. 88 kJ/mol = -13 7.8 6 kJ/mol Under reaction conditions cited , but with no catalyst present, the equilibrium is shifted against the acetic acid. 4 An increase in reaction temperature will cause the equilibrium constant to decrease . For the carbonylation of methanol to occur, a catalyst must be used to give a reasonable yield of acetic acid as product. The Monsanto Company utilize s a rhodium cataiyst in their carbonylation of methanol with carbon monoxid e. Initially, the catalyst used in the carbonylation of methanol