Thiolate complexes synthesis

Both cis- and (rans-structures are possible RuH2(PMe3)4 is cis (Ru-H 1.507, 1.659 A, Ru-P 2.276-2.306 A) [90] while spectra show that RuH2(PF3)4 and others have this configuration. RuH2[PPh(OEt)2]4 is definitely trans (X-ray) with Ru-H 1.6 A, Ru-P 2.272 A. Many diphosphines form dihydrides. Ru(dmpe)2H2 has been a useful starting material for the synthesis of thiolate complexes [91] such as fra s-Ru(SPh)2(dmpe)2. 

Robbins, A.H. and Stout, C.D. (1992) Metallothioneins Synthesis, Structure and Properhes of Metallothioneins, Phytochelatins, and Metal-Thiolate Complexes (eds M.l. ShDman, C.F. Shawlll and KT. Suzuki), VCH Publishers, Weinheim, pp. 31—54. 

The electrochemical synthesis of cadmium and zinc thiolate complexes and their properties were reviewed in addition to other metal ion complexes [152]. 

Stillman MJ, Shaw CF III, Suzuki KT (1992) Metallothioneins. Synthesis, structure, and properties of metallothioneins, phytochelatins and metal-thiolate complexes. VCH Publishers, New York Stratford IJ, Hoe S, Adams GE, Hardy C, Williamson C (1983) Abnormal radiosensitizing and cytotoxic properties of ortho-substituted nitroimidazoles. Int J Radiat Biol 43 31-43 Stubbe J, Kozarich JW (1987) Mechanisms of bleomycin-induced DNA degradation. Chem Rev 87 1107-1136... 

As mentioned above, reactions of this type have been widely used in the synthesis of macrocyclic ligands. Indeed, some of the earliest examples of templated ligand synthesis involve thiolate alkylations. Many of the most important uses of metal thiolate complexes in these syntheses utilise the reduced nucleophilicity of a co-ordinated thiolate ligand. The lower reactivity results in increased selectivity and more controllable reactions. This is exemplified in the formation of an A -donor ligand by the condensation of biacetyl with the nickel(n) complex of 2-aminoethanethiol (Fig. 5-78). The electrophilic carbonyl reacts specifically with the co-ordinated amine, to give a complex of a new diimine ligand. The beauty of this reaction is that the free ligand cannot be prepared in a metal-free reac-... 

M. J. Stilhnan, C. F. Shaw 111, and K. T. Suzuki eds, Metallothioneins Synthesis, Structure, and Properties of Metallothioneins, Phytochelatins and Metal-thiolate Complexes , VCH, New York, 1992. 

Work on Ni-thiolate complexes has focused on the synthesis of mononuclear, S-bridged polynuclear, cluster, and cubane model complexes of relevance to active site in biological systems (see Section 8). Scheme 8 illustrates some of the thiolate complexes that have been prepared. 

The synthesis of homoleptic Ni-thiolate complexes [Ni(L)4] (L = hindered thiolate) has been reported by Armstrong and coworkers. Preparations of nF thiolates... 

The synthesis, structures, and reactivities of metal thiolates with group 4 and 5 metals, and the synthesis and study of copper-thiolates have been reviewed. Hg thiolate chemistry has been reviewed and related to the binding of Hg in vivo by metalloregulatory proteins. A range of two-, three-, and four-coordinate Hg thiolate complexes has been prepared, and comparisons with the metalloregulatory protein, Hg-MerR,... 

The homoleptic sterically hindered thiolate complex [Mo2(TMT)g] containing Mo— Mo triple bonds was first prepared by a multistep reaction (35). The X-ray crystal structure showed a staggered configuration for the thiolate ligands with an Mo— Mo distance of 2.228(1) A (35). They were synthesized subsequently by a simple one-step synthesis involving the reaction of M0CI4 with the TIPT anion in 1,2-dimeth-oxyethane and structurally characterized. A study of their chemistry showed them to be rather unreactive compared with their alkoxide analogues (36). 

Organotin thiolate complexes such as the title compound are useful reagents for the synthesis of transition metal complexes with RS ligands. Examples of this use are given in the procedures that follow this synthesis. 

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