TY - JOUR
T1 - Binuclear Cationic Complexes of Rhodium. 6. Carboxylate and Acetylene Derivatives
AU - Mague, Joel T.
AU - DeVries, Steven H.
PY - 1982
Y1 - 1982
N2 - The A-frame complexes [Rh2(CO)2(µ-C1)(L2)2]PF6 (L2 = (C6H5)2PCH2P(C6H5)2 (DPM), (C6H5)2AsCH2As(C6H5)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)(O2CR')(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)(O2CCH3)(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 (RC2R)(DPM)2](B(C6H5)4)2. The infrared and 1H, 13C, and 31P NMR spectra of these complexes are also discussed.
AB - The A-frame complexes [Rh2(CO)2(µ-C1)(L2)2]PF6 (L2 = (C6H5)2PCH2P(C6H5)2 (DPM), (C6H5)2AsCH2As(C6H5)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)(O2CR')(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)(O2CCH3)(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 (RC2R)(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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U2 - 10.1021/ic00134a071
DO - 10.1021/ic00134a071
M3 - Article
AN - SCOPUS:3643061480
SN - 0020-1669
VL - 21
SP - 1632
EP - 1638
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 4
ER -