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Studien zur C–H‐Aktivierung, VIII, Hydrido(vinyl)rhodium(III)‐Komplexe aus [RhCl(P i Pr 3 ) 2 ] und Olefinen
Author(s) -
Dirnberger Thomas,
Werner Helmut
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250906
Subject(s) - chemistry , rhodium , olefin fiber , methyl vinyl ketone , ethylene , stereochemistry , ketone , monomer , medicinal chemistry , catalysis , organic chemistry , polymer
Studies on C–H Activation, VIII [1] . – Hydrido(vinyl)rhodium(III) Complexes from [RhCl(P i Pr 3 ) 2 ] and Olefins The reaction of [RhCl(P i Pr 3 ) 2 ] n ( 1 ) with methyl vinyl ketone leads to the formation of the olefin complex trans ‐[RhCl(CH 2 = CHC(O)Me)(P i Pr 3 ) 2 ] ( 2 ) which rearranges at ambient temperatures to give the hydrido(vinyl)rhodium(III) isomer( 3 ). From 1 and the α,β‐unsaturated ketones RCH = CHC(O)Me (R = MeO, Me, Ph) the corresponding hydrido(vinyl) derivatives( 5–7 ) are directly obtained. Treatment of 1 with acroleine CH 2 = CHC(O)H gives the olefin complex trans ‐[RhCl(CH 2 = CHC(O)H)(P i Pr 3 ) 2 ] ( 8 ) that does not react by C–H activation but by elimination of ethylene to form the carbonyl compound trans ‐[RhCl(CO)(P i Pr 3 ) 2 ] ( 4 ). The reactions of 1 with CH 2 = CHCO 2 Me, ( E )‐ and ( Z )‐CH(CO 2 Me) = CH(CO 2 Me) afford monomeric ( 10, 12 ) or dimeric ( 14 ) olefin‐rhodium(I) compounds from which 12 is transformed by UV irradiation to give the hydrido(vinyl) isomer( 16 ). Structurally related hydrido(vinyl)rhodium(III) complexes( 17 ) and(P i Pr 3 ) 2 ] ( 20, 21 ) are obtained either directly from 1 and the α,β‐unsaturated carbonyl compound or in two steps via the olefinrhodium(I) precursor. The IR and NMR data of the hydrido(vinyl) compounds prove unambiguously that the vinyl ligand is coordinated by the carbon and the carbonyl oxygen atom.