OLIGOPHOSPHANE LIGANDS .41. OXIDATIVE ADDITIONS OF TRANSITION METAL-HYDROGEN BONDS - REACTIONS OF CPM(CO)(3)H (M=MO, W) WITH [TBUP(CH(2)CH(2)CH(2)PPH(2))(2)]M'CL (M'=RH, IR)

Treatment of (PP2)IrCl[PP2 = tBuP(CH(2)CH(2)CH(2)PPh(2))(2)] with an e quimolar quantity of CpM(CO)(3)H (M = Mo, W) or with HCl in THF result ed in smooth protonation of the d(8) substrate producing [(PP2)Ir(H)Cl ]X (X(-) = [CpMo(CO)(3)](-) (1), [CpW(CO)(3)](-) (2), Cl- (3)). Combin ation of (PP2)IrCl and CPM(CO)(3)H in a 2:1 stoichiometry gave (PP2)Ir (H)Cl-2 (7) together with [(PP2)IrCO][Mo(CO)(3)Cp] (8) or [(PP2)IrCO][ W(CO)(3)Cp] (9). The rhodium analogues (PP2)Rh(H)(2) (4), [(PP2)RhCO][ Mo(CO)(3)Cp] (5), and [(PP2)RhCO][W(CO)(3)Cp] (6) were obtained simila rly from (PP2)RhCl and CpM(CO)3H. Structural assignments for [(PP2)Ir( H)Cl](+) and (PP2)M'(H)Cl-2 (M' = Rh, Ir) as diastereomers in which th e hydride ligand and the tBu substituent on the central phosphorus ato m are located on the same side or on opposite sides of the PP, referen ce plane of the meridionally bound tBuP(CH(2)CH(2)CH(2)PPh(2)](2) liga nd are made on the basis of (i) correlations with known structures and reactivities of similar [(RP(CH(2)CH(2)CH(2)PR(2))(2)M'(H)Cl](+) cati ons and (ii) an X-ray structure determination of 4. The crystal struct ure analysis of a [(PP2)RhCO]+ salt, closely related to 5/6 and 8/9, [ (PP2)Rh(CO)][OCO2H] (10), demonstrates that in the solid state the fou r-coordinate [(PP2)RhCO]+ cation and its counterion exist as essential ly charge-neutralized Rh ... O-contacted ion pairs, two of which are L inked by O-H ... O bridges to centrosymmetric dimers. Ion pairing was also observed by IR spectroscopy for THF solutions of metalates 5/6 an d 8/9.