The Preparation and Low-Frequency Vibrational Spectra of Some Copper(I) and Silver(I) Alkane- and Arene-monothiolate Complexes

Abstract

A number of different methods for preparing anionic Group 1B metal thiolate complexes have been investigated. The compounds [Me4N] [CU2(SMe)3] and [Et4N] [Ag5(SBut)6] are reported for the first time, and new methods for preparing the previously known compounds [Et4N] [Cu5(SBut)6], [Me4N]2 [CU5(SPh)7] and [Et4N]2 [Cu5(SPh)7] are described. The far-infrared spectra of the above compounds, and of CuSMe, CuSBut, AgSBut, [Me4N]2 [CU4(SPh)6] and [Me4N]2 [Ag5(SPh)7] have been obtained, and metal-sulfur stretching bands are assigned in the 150-350 cm-1 region. The low-frequency Raman spectra have also been obtained for some of these compounds. Possible structures for the new compounds are considered in the light of the low-frequency vibrational spectra.

The direct electrochemical synthesis of thiolato complexes of copper, silver, and gold; the molecular structure of [Cu(SC6H4CH3-o)(1,10-phenanthroline)]2•CH3CN

“…Results in the far infrared region should identify v(M-S) modes, and there has been considerable discussion of the frequency range in which these are to be found in the case of copper, zinc, cadmium, and mercury thiolates (19)(20)(21)(22). A major problem, and one which proved difficult in the present work, is that vibrations of the alkyl or aryl group, and of the neutral ligand, obscure much of the region of interest.…”

Surface-Enhanced Raman Spectroscopic Study of Isomeric Formylthiophenes in Silver Colloid

“…The selective enhancement of vibrational modes in the SER spectra of both the isomers has been used as a probe for the determination of the mode of adsorption of each isomer on the metal surface. For instance, metal adsorbate stretching mode such as n(Ag{S) and n(Ag{O) (13)(14)(15) appear in the SER spectra of both the molecules, but the n(C{H) band is only present in 2FT. These observations suggest (16) that 2FT and 3FT molecules are adsorbed on the metal surface through both the sulfur and the oxygen atoms.…”

Synthesis and X‐ray Characterization of Mono‐ and Polynuclear Thiolatocopper(I) Complexes: The Effect of Steric Bulk on Coordination Number and Nuclearity

“…The Cu 5 S 6 -type cluster observed for 4c is less common but is nonetheless similar in its general geometry to other previously reported Cu 5 S 6 core structures that have been obtained mainly from Cu II precursors with aliphatic thiolato ligands exhibiting no significant steric bulk, with higher ligand/ metal stoichiometric ratios. [20,25,31,32] …”

“…[25,31,32] A single Et 4 N + cation counters the cluster charge. Three of the five copper atoms in the cluster of 4c are two-coordinate and two are threecoordinate.…”