132854-52-5Relevant academic research and scientific papers
Synthesis and reactivity of carbonylbis(triphenylphosphine)rhodium(I) complexes of water and weakly coordinating anions
Branan, Daniel M.,Hoffman, Norris W.,McElroy, E. Andrew,Prokopuk, Nicholas,Salazar, Anna B.,Robbins, Martha J.,Hill,Webb, Thomas R.
, p. 1200 - 1207 (2008/10/08)
New complexes trans-Rh(PPh3)2(CO)OPOF2 and [trans-Rh(PPh3)2(CO)(OH2)]Z·nH 2O (Z = SO3CF3, n = 1; Z = BF4, n = 2; Z = ClO4, n = 2) were prepared and characterized. Syntheses of the four species entailed metathesis of the Rh(I) chloride with AgPF6, AgSO3CF3, AgBF4, and AgClO4, respectively, in undried solvents. The water-free OPOF2 complex arises from hydrolysis of a spectroscopically detected Rh(I) PF6- species. Metathesis studies with [N(PPh3)2]+ salts and reactions with pyridine and CO showed the affinity of [Rh(PPh3)2(CO)]+ in CH2Cl2 for ligands L to follow the trend L = (O2CCF3)- > (ONO2)- > pyridine > (OPOF2)- ? H2O ? (SO3CF3)- ≈ (BF4)- ～ (ClO4)-. Monoolefins such as C2H4 and PhCH=CH2 failed to displace the very weakly coordinating ligand H2O from [Rh(PPh3]2(CO)(OH2)]SO3CF 3·H2O in CH2Cl2. The crystal structure of [Rh(PPh3)2-(CO)(OH2)][BF 4]·1/2H2O·1/4C6H12 has been determined. The crystal belongs to the triclinic crystal system, space group P1, with lattice constants a = 11.865 (2) A?, b - 17.235 (6) A?, c = 18.590 (5) A?, α = 91.95 (2)°, β = 101.62 (2)°, γ = 101.83 (2)°, and Z = 4.
