Synthesis and X-ray crystal structures of phosphido-bridged heterobimetallic complexes: [FeIr(mu-CO)(CO)(4)(mu-P(t)Bu(2))((t)Bu(2)PH)] and [CoIr(CO)(5)(mu-H)(mu-P(t)Bu(2))((t)Bu(2)PH)]

From the reaction of [IrCl((t)Bu(2)PH)(3)] (1) with [Fe(CO)(5)] in refluxing toluene, the heterobimetallic complex [FeIr(mu-CO)(CO)(4)(mu-P(t)Bu(2))((t)Bu(2)PH)] (2) is obtained. The X-ray structure investigations of 2 show that the Fe-Ir bond is bridged by a carbonyl group; usually in this special type of complex only a semi-bridging carbonyl ligand bound to the electronically saturated metal center is present. The reaction of [IrCl((t)Bu(2)PH)(3)]/AgPF6 with K[Co(CO)(4)] in acetone at room temperature results in numerous products. From this reaction the phosphido-bridged heterobimetallic system [CoIr(CO)(5)(mu-H)(mu-P(t)Bu(2))((t)Bu(2)PH)] (3) has been isolated. The molecular structures of 2 and 3 were determined by single-crystal X-ray studies: 2 crystallizes in the space group Pbca with eight molecules in the unit cell, 3 crystallizes in the space group P2(1)/n with four molecules per unit cell.