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Treatment of SiCl4 with lithium dithiocarbamates of the formula type Li[R2NCS2] (R = Ph, iPr) in a molar ratio of 1 : 2 afforded the respective six-coordinate silicon(IV) complexes [Ph2NCS2]2SiCl2 (3) and [iPr2NCS2]2SiCl2 (4), which were isolated as the solvates 3·MeCN and 4·MeCN. Compounds 3·MeCN and 4·MeCN were structurally characterised by single-crystal X-ray diffraction and multinuclear NMR spectroscopic studies in the solid state and in solution. In this study, dithiocarbamato ligands were implemented in silicon coordination chemistry for the first time. Compounds 3 and 4 represent the first six-coordinate silicon(IV) complexes with an SiCl2S4 skeleton.

Graphical abstract: Neutral six-coordinate bis(dithiocarbamato)silicon(iv) complexes with an SiCl2S4 skeleton

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