Synthesis and structure of nickel(I) and platinum(I) hydride dimers having identical ancillary ligands

Article abstract of DOI:10.1016/s0020-1693(97)05642-9

The preparation and structures of two new dinuclear hydrides are reported. Reaction of KBEt₃H with the nickel(II) precursor Ni(dippp)Cl₂ (dippp = 1,3 bis(diisopropylphosphino)propane) leads to the formation of the dinuclear complex [(dippp)Ni]₂(μ-H)₂. The single crystal X-ray structure of this Ni(I) dimer shows that the hydrides are symmetrically bridging with the two Ni(dippp) planes staggered with respect to each other by an angle of 75°. The corresponding reaction of KBEt₃H with the platinum(II) precursor Pt(dippp)I₂ leads to the formation of the dinuclear complex [(dippp)PtH]₂. The single crystal X-ray structure of this Pt(I) dimer shows that the hydrides are terminal with the corresponding Pt(dippp) planes orthogonal (92.3°) to each other. The structures of these two Group 10 hydride dimers are compared to the known Pd(I) dimer [(dippp)Pd]₂(μ-H)₂. Crystal data: [(dippp)Ni]₂(μ-H)₂ (1) (C₃₀H₇₀Ni₂P₄), monoclinic, a = 11.513(2), b = 16.420(3), c = 19.696(4) A?, β = 92.40(2)°, Z=4, space group C2lc; [(dippp)PtH]₂ (5) (C₃₀H₇₀P₄Pt₂), triclinic, a = 11.529(1), b = 16.581(1), c = 11.018(2) A?, α = 91.11(1), β = 107.10(1), γ = 106.166(8)°, Z=2, space group P1?. The structures were solved by Patterson and direct methods and were refined by full-matrix least-squares procedures to R = 0.0503 and 0.042 (R_w = 0.0565 and 0.038) for 2487 and 6189 reflections, respectively.