Syntheses of [Pt6(CO)8(SnCl2)(SnCl3)4]4– and [Pt6(CO)8(SnCl2)(SnCl3)2(PPh3)2]2– Platinum–Carbonyl Clusters Decorated by SnII Fragments

Abstract

The reaction of [Pt6(CO)6(SnCl2)2(SnCl3)4]4– (1) with CO under atmospheric pressure resulted in the new [Pt6(CO)8(SnCl2)(SnCl3)4]4– (2) cluster by the addition of two CO ligands and the elimination of a stannylene SnCl2 group. In turn, 2 reacted with 2 equivalents of PPh3 under a CO atmosphere to afford [Pt6(CO)8(SnCl2)(SnCl3)2(PPh3)2]2– (3) by elimination of two stannyl [SnCl3]– ligands. Conversely, the reaction of 2 with 2 equivalents of PPh3 under a N2 atmosphere resulted in a species tentatively formulated as [Pt6(CO)5(SnCl2)2(SnCl3)2(PPh3)2]2– (4–5CO) on the basis of 13C NMR, 31P NMR spectroscopy and ESI‐MS studies. Compounds 2–4 were spectroscopically characterized by IR spectroscopy and multinuclear (13C and 31P) variable‐temperature NMR spectroscopy. The crystal structures of 2 and 3 were determined by means of single‐crystal X‐ray diffraction, and their bonding was computationally investigated by DFT calculations. The possible structure of 4–5CO was predicted by means of DFT methods.