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syn‐Tri‐μ‐chlorido‐bis{[(R,R)/(S,S)‐2,2′‐bis(diphenylphosphino)‐1,1′‐biphenyl]hydridoiridium(III)} tetrafluoridoborate dichloromethane disolvate
Authors:Lutz Dahlenburg  Frank W Heinemann  Dagmar Kramer  Ralf Menzel
Abstract:In the structure of the title compound, Ir2Cl3H2(C36H28P2)2]BF4·2CH2Cl2, the bimetallic cation features a confacial bioctahedral structure that is held together by three bridging chloride ions and is very close to C2 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) Å] are significantly longer than those opposite the Ir—P linkages 2.4287 (7)–2.4672 (8) Å]. The Ir—P distances vary between 2.2464 (9) and 2.2565 (8) Å. This study illustrates the usefulness of sterically demanding biaryl‐based P2 ligands in the synthesis of halide‐bridged Ir2 complexes, which are valuable precursors of versatile catalysts for homogeneous C=O hydrogenation.
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