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Stepwise metal-assisted conversion of η2-CSe2 to η1-Se2CPEt3, η2-Se2CO, and η2-Se2. Crystal structures of the complexes [(triphos)Rh(Se2CO)]BPh4·0.5CH2Cl 2·0.5C4H9OH ...
Bianchini, Claudio,Masi, Dante,Mealli, Carlo,Meli, Andrea,Sabat, Michal,Vizza, Francesco
, p. 3716 - 3721 (2008/10/08)
Full title: Stepwise metal-assisted conversion of η2-CSe2 to η1-Se2CPEt3, η2-Se2CO, and η2-Se2. Crystal structures of the complexes [(triphos)Rh(Se2CO)]BPh4·0.5CH2Cl 2·0.5C4H9OH and [(triphos)Rh(μ-Se2)2Rh(triphos)](BPh4) 2·2DMF [triphos = MeC(CH2PPh2)3]. The reaction of (triphos)RhCl(η2-CSe2) (1) in CH2Cl2 with PEt3 gives the phosphoniodiselenoformate complex (triphos)RhCl(Se2CPEt3) (2). Compound 2 reacts at room temperature in CH2Cl2 solution with dioxygen to yield OPEt3 and (triphos)-RhCl(Se2CO) (3). The chloride ligand can be removed from 3 in CH2Cl2 by NaBPh4 in 1-butanol to give the 16-electron complex [(triphos)Rh(Se2CO)]BPh4·0.5CH2Cl 2·0.5C4H9OH (4), which photochemically or thermally undergoes the chelotropic elimination of CO to form the bis(μ-diselenium) complex [(triphos)Rh(μ-Se2)2Rh(triphos)](BPh4) 2·2DMF (5b). The crystal structures of 4 and 5b have been determined by X-ray crystallography. 4 crystallizes in the triclinic system, space group P1, with a = 18.853 (6) A?, b = 16.744 (5) A?, c = 11.021 (3) A?, α = 69.45 (2)°, β = 81.23 (2)°, γ = 77.35 (2)°, and Z = 2. The structure was refined to an R factor of 0.071 (Rw, = 0.072) for 4093 unique reflections. The structure consists of monomeric complex cations [triphos)Rh(Se2CO)]+, BPh4- anions, and some amount of CH2Cl2 and 1-butanol molecules of crystallization. The metal atom is five-coordinated by the three phosphorus atoms of triphos and by the two selenium atoms of the diselenocarbonate ligand in a distorted-square-pyramidal environment. 5b crystallizes, in the triclinic system, space group P1, with a = 16.950 (5) A?, b = 13.710 (4) A?, c = 13.379 (4) A?, α = 90.19 (1)°, β = 98.53 (2)°, γ = 104.03(2)°, and Z = 1. The structure was refined to a final R factor of 0.053 (Rw = 0.057) for 5458 unique reflections. The structure consists of binuclear [(triphos)Rh(μ-Se2)2Rh(triphos)]2+ cations, BPh4- anions, and DMF molecules of crystallization. The system consists of two (triphos)Rh(η2-Se2) fragments related by a crystallographic inversion center. Each rhodium atom is coordinated by the three phosphorus atoms of triphos, an η2-diselenium molecule, and one selenium atom from the other (triphos)Rh(η2-Se2) moiety.
