TY - JOUR
T1 - Binuclear Cationic Complexes of Rhodium(I) and Iridium(I) Containing Both Carbonyl and Isocyanide Ligands
AU - Mague, Joel T.
AU - Devries, Steven H.
PY - 1980
Y1 - 1980
N2 - The reactions of tert-butyl isocyanide with the A-frame complexes [Rh2(CO)2Cl(L2)2]X and [Ir2(CO)3Cl(L2)2]X (L2 = bis(diphenylphosphino)methane (DPM), bis(diphenylarsino)methane (DAM); X = B(C6H5)4-, BF4-, PF6-) are described. With rhodium, the complexes [Rh2(CO)2(t-C4H9NC)Cl(DAM)2]PF6, [Rh2(CO)(t-C4H9NC)2Cl(DAM)2]B(C6H5)4, [Rh2(CO)2(t-C4H9NC)Cl(DPM)2]B(C6H5)4, and [Rh2(CO)(t-C4H9NC)2Cl(DPM)2]B(C6H5)4 result when 1 or 2 equiv of isocyanide are used. The last two contain bridging carbonyl and chloride ligands while in the first two all the ligands are terminal. The use of excess isocyanide and NaB(C6H5)4 yields [Rh2(t-C4H9NC)4(L2)2](B(C6H5)4)2 which reacts further with CO and SO2 to yield [Rh2(μ-L)(t-C4H9NC)4(L2)2](B(C6H5)4)2 (L = CO, SO2). With iridium, the complexes [Ir2(CO)3(t-C4H9NC)Cl(L2)2]X, [Ir2(CO)2(t-C4H9NC)2Cl(L2)2]X L2 = DPM, X = B(C6H5)4-; L2 = DAM, X = BF4-), and [Ir2(CO)(t-C4H9NC)4(L2)2](B(C6H5)4)2 are obtained. The infrared, 13C and 31P NMR, and the electronic spectra of the complexes are discussed.
AB - The reactions of tert-butyl isocyanide with the A-frame complexes [Rh2(CO)2Cl(L2)2]X and [Ir2(CO)3Cl(L2)2]X (L2 = bis(diphenylphosphino)methane (DPM), bis(diphenylarsino)methane (DAM); X = B(C6H5)4-, BF4-, PF6-) are described. With rhodium, the complexes [Rh2(CO)2(t-C4H9NC)Cl(DAM)2]PF6, [Rh2(CO)(t-C4H9NC)2Cl(DAM)2]B(C6H5)4, [Rh2(CO)2(t-C4H9NC)Cl(DPM)2]B(C6H5)4, and [Rh2(CO)(t-C4H9NC)2Cl(DPM)2]B(C6H5)4 result when 1 or 2 equiv of isocyanide are used. The last two contain bridging carbonyl and chloride ligands while in the first two all the ligands are terminal. The use of excess isocyanide and NaB(C6H5)4 yields [Rh2(t-C4H9NC)4(L2)2](B(C6H5)4)2 which reacts further with CO and SO2 to yield [Rh2(μ-L)(t-C4H9NC)4(L2)2](B(C6H5)4)2 (L = CO, SO2). With iridium, the complexes [Ir2(CO)3(t-C4H9NC)Cl(L2)2]X, [Ir2(CO)2(t-C4H9NC)2Cl(L2)2]X L2 = DPM, X = B(C6H5)4-; L2 = DAM, X = BF4-), and [Ir2(CO)(t-C4H9NC)4(L2)2](B(C6H5)4)2 are obtained. The infrared, 13C and 31P NMR, and the electronic spectra of the complexes are discussed.
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U2 - 10.1021/ic50214a034
DO - 10.1021/ic50214a034
M3 - Article
AN - SCOPUS:4243579016
SN - 0020-1669
VL - 19
SP - 3743
EP - 3755
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 12
ER -