Syntheses of [Pt 6 (CO) 8 (SnCl 2 )(SnCl 3 ) 4 ] 4– and [Pt 6 (CO) 8 (SnCl 2 )(SnCl 3 ) 2 (PPh 3 ) 2 ] 2– Platinum–Carbonyl Clusters Decorated by Sn II Fragments

The reaction of [Pt 6 (CO) 6 (SnCl 2 ) 2 (SnCl 3 ) 4 ] 4– ( 1 ) with CO under atmospheric pressure resulted in the new [Pt 6 (CO) 8 (SnCl 2 )(SnCl 3 ) 4 ] 4– ( 2 ) cluster by the addition of two CO ligands and the elimination of a stannylene SnCl 2 group. In turn, 2 reacted with 2 equivalents of PPh 3 under a CO atmosphere to afford [Pt 6 (CO) 8 (SnCl 2 )(SnCl 3 ) 2 (PPh 3 ) 2 ] 2– ( 3 ) by elimination of two stannyl [SnCl 3 ] – ligands. Conversely, the reaction of 2 with 2 equivalents of PPh 3 under a N 2 atmosphere resulted in a species tentatively formulated as [Pt 6 (CO) 5 (SnCl 2 ) 2 (SnCl 3 ) 2 (PPh 3 ) 2 ] 2– ( 4 – 5 CO) on the basis of 13 C NMR, 31 P NMR spectroscopy and ESI‐MS studies. Compounds 2 – 4 were spectroscopically characterized by IR spectroscopy and multinuclear ( 13 C and 31 P) 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 – 5 CO was predicted by means of DFT methods.