Relationship between electronic structure and geometry of silanethiols and their derivatives: Elucidation of copper group silanethiolates

X-ray structures of known copper group metals' trialkoxysilanethiolates and trialkyl(aryl)silanethiolates are reviewed and their common features described. Total Mulliken charge of the whole silanethiolato rest gives relatively good correlation with the shortening of the Si-S bond lengths. Characteristic tendency to form homoleptic tetramers [{R3SiSM}4] (R = alkyl, aryl or alkoxy group) or mononuclear heteroleptic complexes R3SiSMLn (M = Cu, Ag, Au, L = phosphine or amine, n = 1-3) is discussed in terms of frontier orbitals' properties of the R3SiSM fragment.