Inorganic Chemistry p. 1632 - 1638 (1982)
Update date:2022-08-05
Topics:
Mague, Joel T.
DeVries, Steven H.
The A-frame complexes [Rh2(CO)2(μ-Cl)(L2)2]PF 6 (L2 = (C6H5)2PCH2P(C6H 5)2 (DPM), (C6H5)2AsCH2As(C6H 5)2 (DAM)) react with silver carboxylates to yield the carboxylate-bridged dimers [Rh2(CO)2(μ-O2CR)(L2) 2]PF6 (L2 = DPM, R = CH3; L2 = DAM, R = CH3, C2H5). All three complexes rapidly exchange carbon monoxide at room temperature, but only for the phosphine complex could a μ-carbonyl adduct be detected. Reaction of the carboxylate dimers with electronegatively substituted acetylenes yields the vinylidene-bridged species [Rh2(CO)(μ-CO)(μ-RC2R)(O 2CR′)(L2)2]PF6 (L2 = DPM, DAM, R = CO2CH3, CF3, R′ = CH3; L2 = DAM, R = CO2CH3, CF3, R′ = C2H5). These in turn react with other ligands L (L = CNC(CH3)3, P(OCH3)3) to yield [Rh2(L)(μ-CO)(μ-RC2R)(O2CCH 3)(L2)2]PF6. The complex [Rh2(CNC-(CH3)3)4(DPM) 2](B(C6H5)4)2 also reacts with electronegatively substituted acetylenes to give [Rh2(CNC(CH3)3)4-(RC 2R)(DPM)2](B(C6H5)4) 2. The infrared and 1H, 13C, and 31P NMR spectra of these complexes are also discussed.
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Doi:10.1016/S0040-4039(00)87743-6
(1982)Doi:10.1021/jo00345a039
(1982)Doi:10.1021/om00064a016
(1982)Doi:10.1021/jo00347a023
(1982)Doi:10.1021/ic00135a066
(1982)Doi:10.1021/jo00347a027
(1982)
