The reactions of dirhenium complexes with tris(diphenylphosphino)methane. The conversion of the dirhenium(III) complex cis-Re 2(O 2CCH 3) 2Cl 4(py) 2 to mononuclear trans-ReCl 2[ η2-HC(PPh 2) 3] 2

Abstract

The reaction of tris(diphenylphosphino)methane (HC(PPh 2) 3, abbreviated tripod) with Re 2Cl 4(PMe 3) 4 in hot ethanol leads to the formation of Re 2Cl 4(μ-dppm)(PMe 3) 2 as the major product (dppm = Ph 2PCH 2PPh 2). The compound trans-ReCl 2[ η 2-HC(PPh 2) 3] 2 was obtained as a minor product from the reaction of cis-Re 2(O 2CCH 3) 2Cl 4(py) 2 with HC(PPh 2) 3. This complex, which was structurally characterized by X-ray crystallography, is an example of a small but growing class of mononuclear rhenium(II) complexes that have a trans-ReCl 2P 4 octahedral geometry. Crystal data at +20 °C: triclinic space group P 1 (No. 2), a = 10.867(1), b = 13.157(1), c = 13.4060(9) A ̊ , α = 109.279(6), β = 98.477(5), γ = 112.198(6)°, V = 1591.9(6) A ̊ 3, Z = 1 . The structure was refined by full-matrix least-squares to R = 0.034 ( R w = 0.043) for 5005 data with I>3 σ( I).