Thiolates dinuclear complexes

Thiolate-Pt11 complexes, in particular dinuclear thiolate and dithiolate bridged complexes, have been prepared and characterized a catalyst precursor in hydroformylation reactions for use as.127,128... 

These are formed mainly between metal atoms in d3-cP dinuclear complexes for which perhaps the most important group comprises the ethane-like X3M=MX3 (Dm) compounds, where X = alkyl, amide, alkoxide, thiolate, selenate, and mixtures thereof.115 The synthetic entry into these compounds involves principally the reactions of M2(NMe2)6, as shown in Fig. 18-C-20, and these in turn are made by metathetic reactions involving either MoC13 or WCL, and LiNMe2. 

Ooi and co-workers adopted an elegant synthetic approach to the mixed-metal complexes of 4-methylpyridine-2-thiolate (4-mpyt). This approach includes the initial preparation of mononuclear complexes [M(4-mpytH)4]Cl2 (M = Pt, Pd), in which all four 4-mpytH ligands coordinate to with sulfur-donor atoms (84,102). The structure of the mononuclear Pd(II) complex with nonsubstituted pyridine-2-thiolate, [Pd(pytH)4]Cl2, is shown in Fig. 16 (84). These mononuclear complexes can be further reacted with the second metal ion to give mixed-metal dinuclear complexes. 

The reaction of RhCls with an excess of the anion of TIPT in MeCN also generated a dinuclear complex in high yield, in which the bridging aromatic thiolate also binds via an arene substituent, but in this case the two rhodium atoms are not equivalent (76). A representation of the overall crystal and molecular structure is shown in Fig. 18. A simplified view of the coordination sphere of one rhodium atom is shown in Fig. 19. The structure comprises two distinct metal atoms, with... 

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