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Dahlenburg L, Heinemann FW, Kramer D, Menzel R: syn-Tri-mu-chlorido-bis{[(R,R)/(S,S)-2,2'-bis (diphenylphosphino)-1,1'-biph enyl] hydridoiridium (III)} tetrafluoridoborate dichloromethane disolvate. Acta Crystallogr C. 2008 Mar;64(Pt 3):m144-6. Epub 2008 Feb 23.
In the structure of the title compound, [Ir (2) Cl (3) H (2)(C (36) H (28) P (2))(2)] BF (4) x 2 CH (2) Cl (2), the bimetallic cation features a confacial bioctahedral structure that is held together by three bridging chloride ions and is very close to C (2) symmetric. The hydrides are in a syn orientation (trans to the same halide bridge), and the chelating bis (phosphine) atropisomers display a racemic (R,R)/(S,S) configuration. Because of the high trans-bond-weakening influence of the hydride ligands, the Ir-Cl bonds trans to Ir-H [2.5262 (7) and 2.5365 (7) A] are significantly longer than those opposite the Ir-P linkages [2.4287 (7)-2.4672 (8) A]. The Ir-P distances vary between 2.2464 (9) and 2.2565 (8) A. This study illustrates the usefulness of sterically demanding biaryl-based P (2) ligands in the synthesis of halide-bridged Ir (2) complexes, which are valuable precursors of versatile catalysts for homogeneous C=O hydrogenation. |
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