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Download Bioinorganic Chemistry by Stephen R. Cooper, Simon C. Rawle (auth.) PDF

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 by way of Voltammetry

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3 Gold In aqueous acetone 9S3 reacts with [AuCl(thiodiglycol)] to give {[AuCI(9S3)]}x [,141]. This oligomeric compound features square planar coordination at the Au atoms. Each Au binds to one S atom from a 9S3 molecule, which must twist into a strained conformation ([225] in the nomenclature of Dale) [-76]. Trans to this S atom lies the C1-. Bonds to two trans Au atoms completes the AuSC1Au2 coordination sphere about any given Au ion, and results in a nearly linear infinite polymer. N M R studies in solution indicate interaction of the Au ion with three S atoms that are equivalent on the NMR time scale (at least down to 240 K).

Rawle S~Cu--S I • | ,. _ f . s. ~ Rh• n =3,2,1 Fig. 8. Complexesof 12S3 Table 1) [121]. Unlike [Ni(12S3)2] 2+, however, the Ru(II) complex resists attack by water; indeed, it can be recrystallized from it. As in the case of the 9S3 complex, this difference probably reflects thermodynamic factors as well as the obvious kinetic ones. 03 ,~, comparable with the difference found in the corresponding Ni(II) complexes (Table 1) [121]. MeOH [Ru(Me/SO)6] 2+ + 212S3 [Ru(12S3)/] 2+ ~ , [Ru(12S3)2] 2+ [Ru(12S3)2] 3+ + e- (18a) (18b) Optical spectroscopic studies on the d 6 species [Ru(12S3)2] z+ (Table 3) yield a value of A, the ligand field splitting, 29570 cm- 1, little different from that of the 9S3 analogue (30760 cm-1).

03 ,~, comparable with the difference found in the corresponding Ni(II) complexes (Table 1) [121]. MeOH [Ru(Me/SO)6] 2+ + 212S3 [Ru(12S3)/] 2+ ~ , [Ru(12S3)2] 2+ [Ru(12S3)2] 3+ + e- (18a) (18b) Optical spectroscopic studies on the d 6 species [Ru(12S3)2] z+ (Table 3) yield a value of A, the ligand field splitting, 29570 cm- 1, little different from that of the 9S3 analogue (30760 cm-1). Despite the close similarity in electronic spectra, the two complexes differ appreciably in their electrochemical behavior.

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