# Bimetallic Perthiocarbonate Complexes of Cobalt: Synthesis, Structure and Bonding

## TL;DR

This paper reports the synthesis and characterization of a new bimetallic perthiocarbonate complex of cobalt, revealing its unique structure and bonding.

## Contribution

The synthesis and structural characterization of a novel bimetallic perthiocarbonate complex of cobalt is presented.

## Key findings

- The bimetallic perthiocarbonate complex contains a four-membered metallaheterocycle with a [CS4]2− unit and a [S2]2− unit.
- The complex was characterized using multinuclear NMR, IR, mass spectrometry, and X-ray diffraction.
- Computational analysis provided insights into the bonding of the perthiocarbonate complex.

## Abstract

The syntheses and structural elucidation of bimetallic thiolate complexes of early and late transition metals are described. Thermolysis of the bimetallic hydridoborate species [{Cp*CoPh}{µ-TePh}{µ-TeBH3-ĸ2Te,H}{Cp*Co}] (Cp* = ɳ5-C5Me5) (1) in the presence of CS2 afforded the bimetallic perthiocarbonate complex [(Cp*Co)2(μ-CS4-κ1S:κ2S′)(μ-S2-κ2S″:κ1S‴)] (2) and the dithiolene complex [(Cp*Co)(μ-C3S5-κ1S,S′] (3). Complex 2 contains a four-membered metallaheterocycle (Co2S2) comprising a perthiocarbonate [CS4]2− unit and a disulfide [S2]2− unit, attached opposite to each other. Complex 2 was characterized by employing different multinuclear NMR, infrared spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Preliminary studies show that [Cp*VCl2]3 (4) with an intermediate generated from CS2 and [LiBH4·THF] yielded thiolate species, albeit different from the cobalt system. Furthermore, a computational analysis was performed to provide insight into the bonding of this bimetallic perthiocarbonate complex.