Carbonylate anion [(μ-H)Os3(CO)10L]− as a precursor in the synthesis of heterometallic Os3M clusters

A new method for the synthesis of heterometallic clusters Os3M is developed. The reactions of hydridocarbonyl cluster (μ-H)2Os3(CO)10 (I) with binuclear carbonyls Co2(CO)8 and Fe2(CO)9 in the presence of 1,4-diazabicyclo[2.2.2]octane (Dabco) afford anionic complexes [Os3Co(CO)13]− (II) and [HOs3Fe(CO)13] (III) with the counterion N2C6H13+. Similar reactions with halide complexes [MCp*Cl2]2 (M = Rh and Ir) yield neutral complexes [Os3M(CO)10(μ-H)(μ-Cl)] (M = Rh(IV) and Ir(V)). The reactions occur rapidly at room temperature with high yields. The newly obtained clusters are characterized by the data of IR and 1H NMR spectroscopy, elemental analysis, and X-ray diffraction analysis.