Structure of [RhCl(H)((C6H5)2PCH2P(C 6H5)2)2][B(C6H 5)4]: A rhodium(III) hydrido complex containing chelating bis(diphenylphosphino)methane ligands

Article abstract of DOI:10.1021/ic50195a006

The reaction of the anionic species [RhCl₂(CO)₂]^- with bis(diphenylphosphino)methane (DPM) yields two different products depending on the DPM:Rh molar ratio. An X-ray crystallographic study of the product, obtained with a 2:1 molar ratio of DPM-Rh, proved it to be [RhCl(H)((C₆H₅)₂PCH₂P(C ₆H₅)₂)₂][B(C₆H ₅)₄], a monomeric species containing chelating DPM ligands and mutually trans chloro and hydrido ligands. The complex crystallizes in the space group C_2h⁵-P2₁/c in a cell of dimensions a = 19.477 (2) ?, b = 15.266 (2) ?, c = 22.282 (2) ?, and β = 106.85 (1)° with Z = 4. On the basis of 6832 unique reflections the structure was refined by full-matrix, least-squares techniques to agreement indices of R = 0.064 and R_w = 0.084. Some relevant metric parameters are Rh-P(av) = 2.329 (3) ?, Rh-Cl = 2.465 (2) ?, Rh-H(1) = 1.51 (7) ?, P(1)-Rh-P(2) = 72.47 (6)°, P(3)-Rh-P(4) = 72.43 (7)°, and H(1)-Rh-Cl = 172 (3)°. The Rh-P-C-P chelate frames are not planar, having the methylene groups approximately 0.338 (7) ? out of their respective P-Rh-P planes.