By Stephen R. Cooper, Simon C. Rawle (auth.)
Contents: S.R. Cooper, S.C. Rawle, Oxford, united kingdom: Crown Thioether ChemistryD.M.P. Mingos, L. Zhenyang, Oxford, united kingdom: Hybridization Schemes for Co-ordination and Organometallic CompoundsL. Banci, I. Bertini, Florence; C. Luchinat, Bologna, Italy: The 1H NMR Parameters of Magnetically Coupled Dimers - The Fe2S2 Proteins as an ExampleF.A. Armstrong, Oxford, united kingdom: Probing Metalloproteins via Voltammetry
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Extra resources for Bioinorganic Chemistry
9. R. Cooper and S. C. Rawle the meso isomer all 12 of the C-E bonds assume gauche placement, whereas in the isomeric racemic structure, only eight of the 12 do so. Since aza macrocycles preferentially assume anti placement at the C-N atom bonds, the stereochemical difference found for complexes of 18S6 and 18N6 parallels the conformational preferences of the component carbon-heteroatom bonds [145, 147]. 1 Nickel In the picrate salt of [Ni(18S6)] 2+ the ligand envelops a high-spin Ni(II) ion to yield an octahedral N i S 6 coordination sphere (Fig.
10a), in which a Rh(III) ion nestles between two tridentate 9S3 rings ([3 + 3] coordination) (Fig. 6; Table 1) [-128, 129, 130, 131]. The RhS 6 coordination sphere closely approaches octahedral symmetry, as expected from the high ligand field stabilization energy associated with a low-spin d 6 ion. Metal-sulfur distances compare closely with those in the isoelectronic [Ru(9S3)2] 2+ cation (Table 1). Thus, as in the congeneric Co(III) and Fe(II) complexes, the difference in charge exerts minimal effect on the coordination spheres.
Tetrahedral coordination could also be effected by slippage of the two rings such that each coordinates in bidentate fashion ([2 + 2] coordination), A case can be made for each of the three possibilities, [-3 + 3], [-3 + 1] and [-2 + 21 coordination. Investigation of other group Ib complexes of 9S3 has recently revealed examples of [-3 + 3] coordination ([-Ag(9S3)2] + [-114-116]) while the dimeric [-Cu2(9S3)3]2+ exhibits [-3 + 1] coordination (Fig. 5; Table 1) 1-117]. The closest approach to I-2 + 2] coordination occurs in [Pd(9S3)2] 2+ [1061, [,PdBr2(9S3)] [,106] and [Pt(9S3)2] 2+ [,107], each of which contains an effectively bidentate 9S3.