115338-91-5Relevant academic research and scientific papers
Silicon-oxygen bond-forming reactions upon addition of silanes and silyl halides to the 16-electron alkoxyiridium complexes trans-ROIr(CO)[P(p-tol)3]2 (R = Me or Ph; p-tol = p-Tolyl). Crystal and molecular structure of H2Ir(CO)(SiMe2Ph)[P(p-tol)3]2
Rappoli, Brian J.,Janik, Thomas S.,Churchill, Melvyn Rowen,Thompson, Jeffrey S.,Atwood, Jim D.
, p. 1939 - 1944 (2008/10/08)
The reactions of silanes and silyl halides with the 16-electron alkoxyiridium complexes trans-ROIr(CO)[P(p-tol)3]2 (R = Me or Ph; p-tol = p-tolyl) are reported. The silanes add oxidatively to the alkoxyiridium complex; the resulting complex undergoes reductive elimination of an alkoxysilane with ultimate formation of H2Ir(CO)(SiR3)[P(p-tol)3]2. Reactions of silyl halides with the alkoxy complex results in formation of silicon-oxygen bonds. The dihydride H2Ir(CO)(SiMe2Ph)[P(p-tol)3]2, which is an active hydrogenation catalyst, was subjected to structural analysis. It crystallizes in the centrosymmetric triclinic space group P1 with a = 10.692 (1) ?, b = 11.199 (2) ?, c = 20.557 (4) ?, α = 75.991 (14)°, β = 84.505 (14)°, γ = 77.503 (11)°, V = 2329 (1) ?3, and Z = 2. Diffraction data (Mo Kα, 2θ = 4.5-45.0°) were collected with a Syntex P21 automated diffractometer; the structure was solved and refined to RF = 4.9% for all 6119 reflections (RF = 3.6% for those 5094 data with |Fo| > 6σ(|Fo|)). The non-hydride ligands occupy expanded sites in an octahedral iridium(III) complex with Ir-P(1) = Ir-P(2) = 2.366 (2) ?, Ir-Si = 2.414 (2) ?, and Ir-CO = 1.900 (8) ?. The SiMe2Ph ligand is trans to a P(p-tol)3 ligand (P(1)-Ir-Si = 146.39 (7)°). The hydride ligands were located and refined; their positions are of limited accuracy, but they lie in mutually cis sites, trans to a P(p-tol)3 ligand (P(2)-Ir-H(1) = 169.2 (21)°) and to the CO ligand (C-(1)-Ir-H(2) = 169.4 (22)°).
