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Bioinorganic Catalysis by Jan Reedijk, Elisabeth Bouwman

By Jan Reedijk, Elisabeth Bouwman

Presents the newest examine effects and indicates new subject matters for interdisciplinary learn of steel ions, catalysis, and biochemical structures. moment version highlights capability functions; contains new chapters on zinc and FeS clusters; offers new X-ray research of metalloenzymes; and extra.

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M. Sernetz, B. Gelle´ri, and J. Hofmann, J. Theor. , 117: 209–230 (1985). T. A. Somorjai, J. Chem. , 65: 765–769 (1988). M. Thomas, Solid State Ionics 32/33: 869–871 (1989). J. Erkelens, Naturwiss 77: 86–87 (1990). C. Walsh, Enzymatic Reaction Mechanisms, W. H. Freeman, San Francisco, p. 29 (1979). C. Bond in The Physical Basis for Heterogeneous Catalysis (E. Drauglis and R. I. ), Plenum Press, New York, pp. 56–58 (1975). M. W. Thomas, Principles and Practice of Heterogeneous Catalysis, VCH, Weinheim (1997).

Outer sphere: M(nϪ1)ϩ ϩ XY i M nϩ ϩ [XY] •Ϫ b. Inner sphere: M (nϪ1)ϩ ϩ XY i M X ϩ Y nϩ • (13) (14) Ligand dissociation can involve either heterolytic or homolytic processes. Most biological processes involve the former, although examples of the latter are known. For example, adenosylcobalamin (vitamin B-12 coenzyme), in association with an appropriate apoenzyme, catalyzes a variety of rearrangements via a 1,2-hydride shift (see Chapter 13). The first step in these reactions is thought to be homolytic dissociation of a CoIIIalkyl bond as shown: L5Co IIICH 2 Ad → L 5 Co II ϩ (AdCH2 )• (15) where L5 ϭ vitamin B-12 nucleus; Ad ϭ adenosyl.

See text for details. Lewis Acid Properties of Zinc 41 Scheme 5 Ester substrates and nonsurfactant alkoxide-bound metal complex. hydrolyzed the substrate than the nonsurfactant homologue 10 (Scheme 5), as a result of the concentration of the lipophilic ester substrate in the micelle. The rate promotion was speculated to be due to the formation of the ternary complex (Figure 4a). , the metal-bound alkoxide; see Figure 4b) may yield an acyl transfer intermediate, which is quickly hydrolyzed by a metal-bound OHϪ (or water) to form micellar ligand and metal-picolinate (see Figure 4c).

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