Reactions of [Pt6(CO)6(SnX2)2(SnX3)4] 4– (X = Cl, Br) with Acids: Syntheses and molecular structures of [Pt12(CO)10(SnCl)2(SnCl2)4{Cl2Sn(μ-OH)SnCl2}2]2- And [Pt7(CO)6(SnBr2)4{Br2Sn(μ-OH)SnBr2}{Br2Sn(μ-Br)SnBr2}]2- Platinum carbonyl clusters decorated by Sn(II)-Fragments

The reactions of [Pt6(CO)6(SnX2)2(SnX3)4]4– (X = Cl, 1; Br, 2) with an excess of HBF4·Et2O afforded the new [Pt12(CO)10(SnCl)2(SnCl2)4{Cl2Sn(μ-OH)SnCl2}2]2– (3) and [Pt7(CO)6(SnBr2)4{Br2Sn(μ-OH)SnBr2}{Br2Sn(μ-Br)SnBr2}]2– (4) heterometallic clusters. The molecular structures of 3 and 4 were determined by means of single crystal X-ray diffraction. The bonding within these bimetallic Pt–Sn clusters were investigated computationally by means of DFT methods and Atoms-In-Molecules analyses. 3 and 4 displayed a low valent Pt core stabilised by the interaction with CO and Sn(II) based ligands. The solid state structures of these clusters revealed the presence on H-bonds involving the OH-groups of the {X2Sn(μ-OH)SnX2}– ligands.