Metal chalcogenide nanoclusters with ‘tailored’ surfaces via ‘designer’ silylated chalcogen reagents

Abstract

Silylated chalcogen reagents are proven entry points for the preparation of ligandstabilized, nanometre-sized metal-chalcogen clusters. More recently, these reagents have been developed to incorporate specific functionalities onto the surfaces of nanoclusters. The group 11 metals Cu and Ag in particular yield a wealth of structural types, the features for which are dependent on the nature of the surface chalcogenolate ligands. The content of this review focuses on complexes that have been structurally characterized by single-crystal X-ray diffraction studies and illustrates the ease by which these frameworks can be assembled.

A ferrocenylmethylselenolate complex of Ag(i): preparation of the polyferrocenyl cluster [Ag8(SeCH2Fc)8(PPh3)4] from the new silylated reagent FcCH2SeSiMe3

“…Single crystal X-ray diffraction measurements were performed on either Enraf-Nonius KappaCCD (3,5) or STOE-STADI4 CCD (4) X-ray diffractometers in a cold nitrogen stream using graphite-monochromated Mo-Ka radiation (l = 0.71073 A ˚). Molecular structures were determined via direct methods (SHELXS-97) and refined by a full matrix least squares method based on F 2 using SHELXTL 6.1 software.…”

“…The use of silylated reagents has been shown to be very effective at incorporating a tailored surface onto metal-chalcogen clusters. 5 The size of the cluster product obtained in the reactions of silylated chalcogen reagents with metal salts often depends on the ratio of starting reagents, the steric demands of the chalcogenolate ligand and that of ancillary ligands used. 6 Silylated chalcogen reagents of the type RESiMe 3 (R = organic group; E = S, Se, Te) are soluble in most common organic solvents and have the benefit of introducing various functionalities, ''R'', into metal-chalcogen architectures.…”

A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations

“…In pursuit of metal chalcogenide clusters, Group 11 elements (Cu, Ag, Au) are frequently employed in the synthesis of novel clusters [ 1 , 2 , 3 , 4 ]. Silver chalcogenide clusters have rich structural varieties which can be synthesized by many different approaches [ 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. The primary strategy is the reaction of different Ag(I) precursors with highly reactive silylated chalcogen reagents E(SiMe 3 ) 2 (E = S, Se, Te) [ 5 ], which can afford S 2− /Se 2− /Te 2− in the construction of high-nuclearity silver chalcogenide clusters stabilized by phosphine, chalcogenolate, halide, carboxylate, or alkynyl ligands [ 6 , 7 , 8 , 9 , 10 , 11 ].…”

“…Silver chalcogenide clusters have rich structural varieties which can be synthesized by many different approaches [ 5 , 6 , 7 , 8 , 9 , 10 , 11 ]. The primary strategy is the reaction of different Ag(I) precursors with highly reactive silylated chalcogen reagents E(SiMe 3 ) 2 (E = S, Se, Te) [ 5 ], which can afford S 2− /Se 2− /Te 2− in the construction of high-nuclearity silver chalcogenide clusters stabilized by phosphine, chalcogenolate, halide, carboxylate, or alkynyl ligands [ 6 , 7 , 8 , 9 , 10 , 11 ]. Under this guideline, Fenske and his co-workers have structurally characterized many remarkable silver chalcogenide clusters [ 6 , 7 ].…”

Tethered Polynuclear Copper–Chalcogenolate Assemblies Enabled via NHC Ligation

“…Silylated chalcogen reagents of the type RESiMe 3 (R = an organic group, E = S, Se) have been shown to be a convenient source of organo-chalcogenolate (RE  ) in the synthesis of chalcogenoesters and are well-developed for the preparation of metal–chalcogen bonds . With the latter, their utility in coordination chemistry has been confirmed for both the preparation of polynuclear metal–chalcogen (cluster) architectures as well as single metal coordination complexes .…”