Synthesis of diaryl dithiocarbamate complexes of zinc and their uses as single source precursors for nanoscale ZnS

Diaryldithiocarbamate complexes, [Zn(S2CNAr2)2], have been prepared with a view to comparing their structures, reactivity and thermally-promoted degradation with respect to the well-studied dialkyl-derivatives. In the solid-state both [Zn{S2CN(p-tol)2}2] and [Zn{S2CN(p-anisyl)2}2] are monomeric with a distorted tetrahedral Zn(II) centre, but somewhat unexpectedly, the bulkier naphthyl-derivative [Zn{S2CN(2-nap)2}2]2 forms dimeric pairs with five-coordinate Zn(II) centres. Preliminary reactivity studies on [Zn{S2CN(p-tol)2}2] suggests that it binds amines and cyclic amines in a similar fashion to the dialkyl complexes and can achieve six-coordination as shown in the molecular structure of [Zn{S2CN(p-tol)2}2(2,2′-bipy)]. The thermal decomposition of [Zn{S2CN(p-tol)2}2] was studied in oleylamine solution by both heat-up and hot-injection methods. Nanorods of ZnS were produced in both cases with average dimensions of 17 × 2.1 nm and 11 × 3.5 nm respectively, being significantly shorter than those produced from [Zn(S2CNiBu2)2] under similar conditions. This is tentatively attributed to the differing rates of amine-exchange between diaryl- and dialkyl dithiocarbamate (DTC) complexes and/or their differing rates of DTC loss following amine-exchange. The solid-state decomposition of [Zn{S2CN(p-tol)2}2] has also been studied at 450 °C under argon affording irregular and large (10–300 µm) sheet-like particles of wurtzite

Copper diaryl-dithiocarbamate complexes and their application as single source precursors (SSPs) for copper sulfide nanomaterials

Copper diaryl-dithiocarbamate (DTC) complexes have been prepared including [Cu(S2CNAr2)2], [Cu{S2CN(p-tolyl)2}]n and [Cu{S2CN(p-tolyl)2}(PPh3)2] and used as single source precursors to copper sulfide nanomaterials

Synthesis and characterization of tungsten carbonyl complexes containing thioamides

274-280Tungsten pentacarbonyl complexes are isolated from the reactions between [W(CO)5(NCMe)] and thioamides, the former being generated in situ upon addition of  equimolar amount of Me3NO into an acetonitrile solution of W(CO)6. Room temperature reactions between [W(CO)5(NCMe)] and acyclic thioamides such as thioacetamide and benzamide afford [W(CO)5{к1-(S)-RCSNH2}] in which the thioamides are coordinated to tungsten through sulfur. Similar S-coordinated complexes, namely, [W(CO)5{к1-(S)-thiolactam}] are also isolated from the reactions with cyclic thioamides or thiolactams under the same reaction conditions. All the new complexes have been adequately characterized by spectroscopic data together with single crystal X-ray diffraction studies for four complexes

Reactions of [CpM(CO)₃]₂(M = Mo, W) with Ph₃SnSR:Formation of CpM(CO)₃(SnPh₃) and CpM(CO)₂(²-SR) via Sn-S bond cleavage

<div><p>The mixed-metal compounds CpM(CO)₃(SnPh₃) (<b>1</b>, M = Mo; <b>2</b>, M = W) are obtained as the only isolable products from the reactions of [CpM(CO)₃]₂ with PhSSnPh₃, whereas similar reactions with pymSSnPh₃ (pymS = pyrimidine-2-thiolate) lead to the formation of chelate compounds CpM(CO)₂(κ²-pymS) (<b>3</b>, M = Mo; <b>4</b>, M = W). Separate experiments show that CpM(CO)₃(SnPh₃) are precursors of CpM(CO)₂(κ²-pymS). CpM(CO)₃(SnPh₃) can also be synthesized in slightly improved yield from the direct reaction between [CpM(CO)₃]₂ and Ph₃SnH, while the yield of CpM(CO)₂(κ²-pymS) becomes negligible when [CpM(CO)₃]₂ is treated with pymSH.</p></div

Biomimics of [FeFe]-hydrogenases incorporating redox-active ligands:synthesis, redox properties and spectroelectrochemistry of diiron-dithiolate complexes with ferrocenyl-diphosphines as Fe₄S₄ surrogates

Article prepares and characterizes a small series of new [FeFe]-ase biomimics which contain a ferrocenyl diphosphine as a surrogate for the Fe₄S₄ moiety in the H-cluster of the enzyme. Mechanistic details of both proton reduction and H₂ oxidation have been studied by DFT allowing speculative reaction schemes to be developed