New silver cluster compounds containing dithiobenzoate ligands

Abstract

Three new 4-atom silver cluster compounds have been synthesized using two different substituted dithiobenzoate ligands, and their crystal and molecular structures were determined by single crystal X-ray diffraction. Molecules of the complex [Ag 4{2,4,6-(CH 3) 3C 6H 2CS 2} 4py 3]· 1 2 py contain the four silver atoms in a roughly tetrahedral array, each forming three bonds to sulfur atoms, one-half of which bridge two Ag atoms and one-half of which attach to only one Ag atom. Pyridine nitrogens are attached to three of the four silvers. In the complex [Ag 4( o-CH 3C 6H 4CS 4) 4py 4] the four silver atoms are in a very distorted tetrahedral array, each forming three bonds to sulfur atoms, one-half of which bridge two Ag atoms and one-half of which attach to only one Ag atom. Each Ag atom is also coordinated to a pyridine nitrogen. In the third cluster complex, the anion [Ag 4{2,4,6-(CH 3) 3C 6H 2CS 2} 6] 2− contains four silver atoms in a roughly square planar array, each forming four bonds to sulfur atoms, one-third of which bridge two Ag and two-thirds of which attach to only one Ag atom. Although there are AgAg distances in these compounds which fall well within expected single bond distances it is uncertain whether there are (or even can be) substantial bonding interactions between the silver atoms.