Heterometallic Ni-Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

The direct reactions of homometallic [Ni₆(CO)₁₂]^2- and [Pt₆(CO)₁₂]^2- Chini carbonyl clusters result in heterometallic Ni-Pt Chini-type clusters of the general formula [Pt_6-xNi_x(CO)₁₂]^2- (x = 0-6). Their molecular structures have been determined by single-crystal X-ray diffraction (SC-XRD), showing a common octahedral (staggered, D_3d) structure analogous to that of [Ni₆(CO)₁₂]^2-, whereas [Pt₆(CO)₁₂]^2- displays a trigonal-prismatic (eclipsed, D_3h) structure. This structural change after replacing one single Pt with Ni may be classified as an alloying effect, and it has been theoretically investigated by DFT methods. Spectroscopic (IR and ¹⁹⁵Pt and ¹³C NMR) and ESI-MS studies indicate that mixtures of [Pt_6-xNi_x(CO)₁₂]^2- (x = 0-6) clusters are actually present in solution, whose compositions may be varied in an almost continuous way. Thus, they may be viewed as random alloy clusters whose overall compositions depend on the stoichiometry of the reagents.