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Reactions of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine George S

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Reactions of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine George S Eastern Illinois University The Keep Masters Theses Student Theses & Publications 1975 Reactions of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine George S. Leotsakos Eastern Illinois University This research is a product of the graduate program in Chemistry at Eastern Illinois University. Find out more about the program. Recommended Citation Leotsakos, George S., "Reactions of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine" (1975). Masters Theses. 3495. https://thekeep.eiu.edu/theses/3495 This is brought to you for free and open access by the Student Theses & Publications at The Keep. It has been accepted for inclusion in Masters Theses by an authorized administrator of The Keep. For more information, please contact [email protected]. PAPER CER TI FICA TE #2 TO: Graduate Degree Candidates who have written formal theses. SUBJECT: Permission to reproduce theses. t The University Library is receiving a number of requests from other institutions asking permission to reproduce dissertations for inclusion in their library holdings. Although no copyright laws are involved, we feel that professional courtesy demands that permission be obtained from the author before we allow theses to be copied. Please sign one of the following statements: Booth Library of Eastern Illinois University has my permission to lend my thesis to a reputable college or university for the purpose of copying it for inclusion in that institution's library or research holdings. I Date I respectfully request Booth Library of Eastern Illinois University not allow my thesis be reproduced because Date pdm · -���·..- -�_.,_..· -- - --- ·-""'-- -----..,.- ··......-. - '�--- _ · _- -- --- - - - ----- ----- -- . -- -..-. -. -.. -- -.- -- ----- -· · - -·-·- - --..- ---- ·- - --· ·....,..Jl".tc•r•....,.., .,. r 1 • ..• I•It I i.: REACTIONS OF TUNGSTEN CARBONYL COMPLEXES CONTAINING DIPHENYLVINYLPHOSPHINE (TITLE) BY George Leotsakos s. - - THESIS SUBMIITED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF Master of Science in Chemistry IN THE GRADUATE SCHOOL, EASTERN ILLINOIS UNIVERSITY CHARLESTON, ILLINOIS 1975 YEAR I HEREBY RECOMMEND THIS THESIS BE ACCEPTED AS FULFILLING THIS PART OF THE GRADUATE DEGREE CITED ABOVE ??/;J� li>ATE 17.? ADVISER r IDATE --- · -- -·- - I REACTIONS OF TUNGSTEN CARBONYL COMPLEXES CONTAINING DIPHENYLVINYLPHOSPHINE George S. Leots akos Bachelor of Science Eastern Illinois University Charleston , Illinois Au gust, 1971 Submitted in partial ful fillment of the requirements for the degree of Master of Science in Chemistry at the Graduate School of Eastern Illinois University CHARLE STON, ILLINO IS 1975 REACTIONS OF TUNGSTEN CARBONYL CbMPLEXES CONTAINING DIPHENYLVINYL PHOSPHINE Thesis Approved Dr. R. L. Keiter, Thesis Ad visor Dr. D. w. Ebdon Dr. R. H. KEl.,rraker ii . DEDICATION To my Parents iii ACKNOWLEDGEMENT The author wishes to express his sincere apprecia­ tion to Dr. Richard Keiter for suggesting the problem and for his guidance, inspiration , and infinite patience throughout the investigation. The author would like to give thanks to other me mbers of the faculty for their active interest and help. Special thanks are in order for the author's wife, Sherri, for her constant understanding , encouragement and moral support. iv TABLE OF CONTENTS Chapter Page I Introduction • • • • • • • • • • • • • • • • • • 1 II Results and Discussion . ............ 10 III Experimental • • • • • • • • • • • • • • • • • • 33 A. General Considerations and Comments on the Prepar ative Me thod s •••••• • • • 33 • • • • • • • • • • B.. Preparation of Complexes 34 c. Attempted Preparations • • • • • • • • • • • 42 Bibliography • • • • • • • • • • • • • • • • • • • • • 46 v LIST OF FIGURES Figure Page 1. Expanded Infrared Spectrum of (OC) WPPh CH = CH • • • • • • • • • • • • • • • • 11 5 2 2 = 2. NMR Spectrum of (OC) WPPh CH CH • • • • • • • • 14 5 2 2 3 . Expanded Infrared Spectrum of ( OC) wPh PCH CH PPh • • • • • • • • • • • • • • • 16 5 2 2 2 2 4. NMR Spectrum of (OC) wPh PcH cH PPh • • • • • • • 1 7 5 2 2 2 2 s. Expanded Infrared Spectrum of (OC) WPh PcH cH �Ph CH ••.•••.••• • • 20 5 2 2 2 2 3 r- + 6. NMR Spec trum of (OC) WPh PcH cH PPh CH • • • • 21 5 2 2 2 2 3 r- 7. Expanded Infrared Sp�ctrum of (OC) WPh PCH(CH )cH PPh CH •....••••• 23 5 2 3 2 2 3 r- . + 8. NMR Spectrum of (OC) WPh PCH(CH )cH PPh CH I- •• 24 5 2 3 2 2 3 9. Expanded Infrared Spectrum of the Product Resulted after Refluxing (OC) WPh PCH(Li )CH PPh • 26 5 2 2 2 10 . Expanded Infrared Spectrum of the Produc t from the Reac tion (OC) WPh PCH = CH + Br • • • • • • 27 5 2 2 2 11. NMR Spectrum of the Produc t from the Re ac tion = + ( OC) \JPh PCH CH Br • • • • • • • • • • • • • 28 2 2 2 S 12. NMR Spectrum of the Recovered Material from the = Reaction (OC ) WPh PCH CH + PhLi . • • • . • • ·• 30 5 2 2 1 3. NMR Spectrum of the Recovered Material from the = + . Reaction (OC) WPh PCH CH CH Li • • • • • • • 31 5 2 2 3 vi LIST OF TABLES Table Page I Infrared Carbonyl St.retching Frequencie.s of Monosubstituted Pentacarbonyl Complexes ••• • • • 13 vii ABSTRACT Title of Thesis: Reactions of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine Name: George s. Leotsakos Thesis directed by: Dr. Richard L. Keiter N . new synthetic route for the production of the tungsten carbonyl complex (OC ) WPPh cH cH PPh has been 5 2 2 2 2 discovered. It has been found that lithiumdiphenylphosphide rPnr.ts with diphenylvinylohosphinepentacarbonyltunqsten(O) in tet rahydrofuran to produce .upon hydrolysis a good yield of the pentacarbonyl product : THF (OC ) WPPh CH = CH + LiPPh ) (OC ) WPPh CHLiCH PPh 5 2 2 2 5 2 2 2 (OC ) �·1PPh CHLiCH PPh + H 0 ) (OC ) wPPh cH cH PPh + LiOH 5 2 2 2 2 5 2 2 2 ? No evidence for the formation of secondary products was noted nor was there evidence for preferential attack o� the carbonyl group by LiPPh to form a carbene complex. 2 Diphenylvinylphosphinepentacarbonyl tungsten(O) (mp 62-n4 °C) , was prepared for the first time by two differ­ ent me thods . I. Displacement of aniline from anilinepentacarbonyl­ tungsten(O) complex with diphenylvinylphosphine. (OC ) WNH c H + PPh CH = CH ) 5 2 6 5 2 2 (OC) WPPh CH =. CH + c H NH 5 2 2 6 5 2 rl\Am�nt THF fr.om (OC) ,..W HF complex with TT. Di �rl Of ..J (r ) diphenylvinylphosphine. uv W(CO) + THF ) (OC) w HF + CO 6 5 (l' ) (OC ) W HF Ph PCH = CH > (C0 ) WPPh CH = CH + THF 5 � ) + 2 2 5 2 2 Of the two methods the latter produced better yields and eliminated the need for the unstable aniline complex inter- mediate necessary in the former method. CHAPTER I INTRODUCTION Syntheses of transition met al complexes in which a pot entially bidentate ligand serves as a monodentate are un­ 1 common. In 1970 Rigo and co-workers synthesized a five coordinate cobalt complex, Co (Ph PcH cH PPh ) (CN) , in which 2 2 2 2 2 2 one of the diphosphines served as a monodentate ligand. The v;as 1 ig .J.r.d' raported in 1972 by 2 Keiter and Shah from the reaction (OC) wc H NH + PPh CH cH PPh 5 6 5 2 2 2 2 2 ) (OC) WPPh CH cH PPh c H NH 5 2 2 2 2 + 6 5 2 The reaction depends upon the thermodynamic instability 0f 3 the aniline complex. A large excess of the diphos ligand was needed for the reaction, however, in order to· obtain the desired product . If equimolar amounts of ligand to aniline complex were employed for the reaction , a mixture of the dimet al lic compl.:x (OC) �JPPh cH CH ?Ph \J(C0) as well as the 5 2 2 ; 2 5 desired monodentate product was obtained, with the format ion of the first being favored. Att empts to directly synthesize (OC) PPh CH CH PPh from W(C0 ) and diphos photolyt ically or 5 ? 2 ? ? 6 thermally were unsuccess �ul because of the formation ot disubstituted products of the type (OC) (diphos )W. 4 1 2 More rece ntly complexes containing potential chelating ligands as mon?dcntates ·have been synthesized by an alternate me thod in which an anionic carbonyl halide 4 is allowed to react with the diphosphine. The disadvantage of this synthesis lies with the instability of the halogenometalpentacarbonyl complex. 5 It has been the .pur pose of this research to find a ne w synthetic route for the production of (OC) WPPh cH cH PPh • The reaction spec ifically investigated 5 2 2 2 2 involves the addition of an alkali me tal phosphide to a tungsten carbonyl complex containing diphenylvi nyl phosphine ) (OC) WPPh HCH PPh S 2f 2 2 Li > Since (OC) WPPh CH = CH had not bee n previously reported in 5 2 2 the literature , the first task was to determine if the affin- ity of the me tal for the lone pair of phosphorus is greater than the affinity of the me tal for the double bond of the olefinic group. The only complexes of PPh CH = CH 2 2 .c f)Leviou::;ly reporl:ed a e tiio:::>e of Ay (I) .i.n which it is found that both the. phosphorus atom and the double bond· coordinate 6 to give 1:1 and 2:1 co�plexes. and 3 The coordination chemistry of a nu mber of other ligands containing both phos phorus and ol�finic groups has been 7 8 reported.· ' Some examples of these complexes are shown below: Cu CH If It should be noted that in all reported examples , phosphorus is coordinated to the metal wh ereas the double bond may or may not be ccordinated. Other phosphine ligands containing an unsaturated site have been reported to coordinate to the central atom of Group VI metal carbonyls. K. Issleib and 9 coworkers reported that 3-butenyldiethylphosphinepenta- 4 carbonylchromium(O) can be prepared when Cr(C0 ) is irradiated 6 in the presence of 3-butenyldiethylphosphine.
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