Progress in Inorganic Chemistry, Volume 38 by Stephen J. Lippard

By Stephen J. Lippard

A part of a longtime sequence dedicated to chosen themes on the leading edge of inorganic chemistry examine, this quantity explores bioinorganic chemistry. It offers quite a few examples of the applying of inorganic chemistry to organic platforms.

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7-A resolution and is set out in Fig. 10. 9-A resolution) (13, 14) and in pig heart aconitase (115) are quite similar. The most prominent feature of the Dg Fd I1 cluster structure is its close adherence to the voided cubane configuration 3. It might have been expected that, in the process of removing one Fe atom from a cubane-type structure, the product cluster might relax or readjust to a more open or flattened arrangement. With reference to Fig. 25 SI S4' Fe3 Figure 10. The structure of the [3Fe-4S]'+ cluster of Dg Fd 11, including cysteinyl sulfur atoms (9); selected interatomic distances (A) and angles are given.

One-electron reduction of SiR" produces SiR'-, in which siroheme has been reduced to the Fe(I1) level. Further reduction occurs at the cluster to afford the catalytic state SiR2-, of which three substates classified by their EPR spectra are observed (199). These spectra depend on the presence or absence of an additional axial ligand and the identity of that ligand. The distinct EPR spectra of the substates arise from a S = f [4Fe-4SI1+ cluster, the exchange coupling of which is modified by different magnetic properties of the siroheme center.

A. WEIGEL clusters may be obtained that are not necessarily accessible via direct methods (2, 16, 65, 70); that is, from an iron salt, a sulfide source, and thiolate. Ethanethiolate or t-butylthiolate are particulary good precursor ligands for a substitution reaction because the volatile thiol released after reaction may be removed in vucuu, thus driving the reaction to completion. Reaction 3 is a general example of a ligand substitution reaction with an electrophile, EL (71, 72). Acids, acyl halides, and anhydrides have been shown to undergo Reaction 3, generating substitution products in solution.

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