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 through Voltammetry

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Bioinorganic Chemistry

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.

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Cis-[ Co(14S4)(NCS)2 ] + cis-[ Co(14S4)(ox)2 ] + cis-[Co(14S4)(N02)2] + cis-[Rh(14S4)C12] + red-br red or yel CH3NO 2 CHaNO 2 CHaNO 2 H20 [-50] [50] [-50] [50] cis-[,Rh(14S4)Br 2] + cis-[Rh (14S4)I2 ] + yel yel H20 H20 [50] [-50] cis-[Ru(14S4)C1 z ] yel CH3CN [180] cis-[Ru(14S4)C12 ] + red 540(840) 420 528(579) 470(814) 350(2270) 320(sh) 252(26950) 370(2180) 245(24150) 405(2460) 320(8500) 245(22550) 430(sh. 125) 360(1010) 298(1090) 246(sh, 3550) 560(932) 485(sh, 740) 424(1350) 350(sh, 1620) 323(2050) HC1 [180] [Cu(16S4)(OCIO3)2 ] [Mo(SH)2(16S4)212 + [Mo202(16S4)2(OEt)] 3+ [MoO(SH)(16S4)] + fac-[MoCl3(M%-16S4)] bl or bl red-br or bridging 16S4 ~t-O and M o = O Mo-SH, Mo = O CHC1 a [170] [185] [185] [185] [-187] [,MoBr2(Me s"16S4)] [M oCl 2(Me s - 16S4)] or yel 16S4 440(6100) 603(800) 470(3700) 285(21600) 610(6950) 240(16800) 625(200) 505(400) 453(160) 290(2800) 750(25) 320(5900) 495(45) 334(4200) 457(33) CHC13 CHCI 3 [187] [187] [Cu(12S4)(OH2)] 2 + [Cu(13S4)(OH2)] 2+ [Cu (15S4) (OC10 a)2 ] [Ni(benzo- 15S4)] 2+ bl bl bl yel red Miscellaneous 387(6900) 675(2000) 390(6100) 625(1800) 414(8000) 565(1100) 350(1935) 255(20300) 510(273) 450(sh, 1 4 2 ) cis-[Ru(benzo-15S4)Cl2] yel [Ni 2(28S8)] 4 + red [Niz(NCS)4(28S8)] bl-gr cis-[,Rh(benzo-15S4)C12] + 440(sh, 72) 362(984) 284(sh, 1660) 502(210) 440 1010(44) 910(57) 590(47) benzo-15S4; H20 benzo-15S4; CH3NO 2 CH3CN low-spin; sq.

2 ,~; Fig. 10; Table 1) [93]. R. Cooper and S. C. g. picrate [93], BF4) with the ligand in MeNO2 (Eq. 23a). MEN02 Cu(II) + 18S6 , [Cu(18S6)] 2+ (23a) MeCN [Cu(MeCN)4] + + 18S6 , [Cu(18S6)] + (23b) MeNO2 [Cu(18S6)] 2+ + e- , [Cu(18S6)] + (23c) CH2C12/MeCN 2[Cu(MeCN)4 ] + + 18S6 CuCI + 18S6 , [CuCI(18S6)] x , [Cu2(MeCN)2(18S6)] 2 + (23d) (23e) Reduction of [Cu(18S6)] 2+ (or reaction of 18S6 with [Cu(MeCN)4](BF4) ) yields [Cu(18S6)] + (Fig. 10; Eq. 23b, c), in which Cu(i) coordinates tetrahedrally with four thioether groups from one 18S6 molecule (Table 1) [93].

4 Platinum With 18S6 platinum(II) yields [Pt(18S6)] 2+ [108-], which is isostructural and otherwise essentially identical with its Pd(II) analogue (Fig. 10). 1 A (Table 1). 38 A) by over 1 ,~. As in the corresponding Pd(II) complex, the axial S atoms lie off the tetragonal axis by approximately 15°. This angular distortion presumably reflects the conflict between ligand conformational preferences and M-L bonding in determining geometry. g. [Ni(18S6)] 2+) [148]; for Pd(II) and Pt(II), however, where axial ligands bind at most weakly, conformational factors influence the coordination geometry.

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