ISSN:
0009-2940
Keywords:
Rhodium(I) complexes
;
Olefin complexes
;
Hydrido(vinyl)rhodium(III) complexes
;
C-H Activation
;
Carbonyl compounds, α,β-unsaturated, reactions of
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Studies on C-H Activation, VIII[1]. - Hydrido(vinyl)rhodium(III) Complexes from [RhCl(PiPr3)2] and OlefinsThe reaction of [RhCl(PiPr3)2]n (1) with methyl vinyl ketone leads to the formation of the olefin complex trans-[RhCl(CH2 = CHC(O)Me)(PiPr3)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 CH2 = CHC(O)H gives the olefin complex trans-[RhCl(CH2 = CHC(O)H)(PiPr3)2] (8) that does not react by C-H activation but by elimination of ethylene to form the carbonyl compound trans-[RhCl(CO)(PiPr3)2] (4). The reactions of 1 with CH2 = CHCO2Me, (E)- and (Z)-CH(CO2Me) = CH(CO2Me) 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 (PiPr3)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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250906
