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By Stephen J. Lippard

This complete sequence of volumes on inorganic chemistry offers inorganic chemists with a discussion board for severe, authoritative reviews of advances in each quarter of the self-discipline. each quantity reviews contemporary growth with an important, up to date choice of papers via across the world famous researchers, complemented by way of specified discussions and whole documentation. every one quantity contains a whole topic index and the sequence features a cumulative index besides.

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Depending upon the nature of L, as noted elsewhere in this review, these compounds have been observed in addition to undergo ligand atom inversions, 1 ,2-metal shifts, 1,3-metal shifts, and ligand ring reversals. Where values for the free energies of activation for sulfur or selenium inversion have been determined they are noted in Table 11. Various members of the family of complexes [MO~(CO)~(F*-SR)~(~-C,H,),] have been reported (136, 242), often interconverting as a consequence of pyramidal sulfur inversion (57).

B. Rhodium and Iridium. J+Y-, where X = C1, Br, L = MeSCH,CH,SMe, and Y = C1, CIO,, &Os, PF, or B(C6HJ4 (189, 246). The observation of sulfur inversion in these is reported (246). In the particular case of truns[RhCl,(MeSCH2CH2SMe),l+C1-, 41, variable temperature Io3Rh(natural abundance 100%; I = $) NMR studies were used to show the presence of isomers caused solely by slowed inversion about rhodium coordinated sulfur atoms (189). 41 The complex mer-[RhCI3{S(CH2SiMe3),},], 42, is of particular interest in that it has coordinated sulfur atoms of identical ligands in two different chemical THE STEREODYNAMICS OF METAL COMPLEXES OF SULFUR LIGANDS 39 environments in the coordination sphere.

The evidence is based on the observed nonequivalence of methylene protons in the sulfur ligand, but is not very substantial. There is no clear reason why inversion in these weak complexes should be considerably accelerated compared to the free ligand. The pyramidal stability of selenium and tellurium atoms in selenoxides (210, 204), selenonium ions (144), and telluronium ions (144, 186) has been established for many years, and there appear to be no reports of rapid inversion of these atoms in organochalcogen compounds.

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