SYNTHESIS AND CHARACTERIZATION OF SOME NEW COMPLEXES OF THE VASKA-TYPE TRANS-[IRX(CO)L2] (X = CL OR I - L = PHOSPHITE, PHOSPHINITE OR PHOSPHONITE) AND THE DIRECTION OF DIHYDROGEN ADDITION TO THESE SPECIES
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A series of new Vaska-type complexes trans-[IrX(CO)L2] (XCl, LP(OEt)Ph2 (1), P(OEt)2Ph (2), P(O-o-C6H4Ph)3 (3), P(OPri)3 (4), P(OBun)3 (5); XI, LP(OEt)Ph2 (6), P(OEt)2Ph (7), P(O-o-C6H4Ph)3 (8), P(OBun)3 (9) are prepared and characterized. In solution complex 8 undergoes slow cyclometallation to give [IrHI(CO){P(O-o-C6H3Ph)(O-o-C6H4Ph)2} {P(O-o-C6H4Ph)3}] (10). The oxidative addition of H2 to 1-9 occurs stereospecifically with cis addition of H2 parallel to the XIrCO axis rather than perpendicular to the axis, leading to cis, trans-[IrH2X(CO)L2] with a trans disposition of the two L ligands. This direction of H2 addition is not in agreement with a prior suggestion based on ab initio quantum chemical calculations. 1992.
