SCHEDULED MAINTENANCE
Platinum carbonyl clusters stabilized by Sn(ii)-based fragments: syntheses and structures of [Pt6(CO)6(SnCl2)2(SnCl3)4]4−, [Pt9(CO)8(SnCl2)3(SnCl3)2(Cl2SnOCOSnCl2)]4− and [Pt10(CO)14{Cl2Sn(OH)SnCl2}2]2−†
Abstract
The reaction of [Pt15(CO)30]2− with increasing amounts of SnCl2 affords [Pt8(CO)10(SnCl2)4]2− (2), [Pt10(CO)14{Cl2Sn(OH)SnCl2}2]2− (5), [Pt6(CO)6(SnCl2)2(SnCl3)4]4− (3), [Pt9(CO)8(SnCl2)3(SnCl3)2(Cl2SnOCOSnCl2)]4− (4) and [Pt5(CO)5{Cl2Sn(OR)SnCl2}3]3− (R = H, Me, Et, and iPr) (1-R). 1-R and 2 have been previously described, whereas 3–5 are herein reported for the first time. The species 1–3 are the main products of the reaction under different experimental conditions, whereas 4 and 5 are by-products of the synthesis of 3 and 2, respectively. From a structural point of view, the clusters 1–5 all show a perfect segregation of the two metals, which are composed of a low valent Pt core decorated on the surface by Sn(II) fragments such as SnCl2, [SnCl3]−, [Cl2Sn(OH)SnCl2]− and [Cl2SnOCOSnCl2]2−. These fragments behave as two electron donor ligands via each Sn-atom (and also the C-atom in the case of [Cl2SnOCOSnCl2]2−). The [Cl2SnOCOSnCl2]2− ligand is rather unique and may be viewed as a bis-stannyl-carboxylate, a carbon dioxide μ3:k3-C,O,O′-CO2 or a carbonite ion [CO2]2− stabilized by coordination to metal atoms. Compounds 1–5 have been fully characterised via IR spectroscopy, X-ray crystallography and DFT calculations.
![Graphical abstract: Platinum carbonyl clusters stabilized by Sn(ii)-based fragments: syntheses and structures of [Pt6(CO)6(SnCl2)2(SnCl3)4]4−, [Pt9(CO)8(SnCl2)3(SnCl3)2(Cl2SnOCOSnCl2)]4− and [Pt10(CO)14{Cl2Sn(OH)SnCl2}2]2−](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=C5DT04696C&imageInfo.ImageIdentifier.Year=2016)
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