Identification of inner- and outer-sphere reaction pathways in the reduction of iron-sulphur proteins with a chromium(II)-macrocycle complex |
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Authors: | IK Adzamli RA Henderson H Ong AG Sykes R Cammack KK Rao |
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Institution: | Department of Inorganic Chemistry, The University, Newcastle-upon-Tyne, NE1 7RU, England.;Department of Plant Science, King''s College, London, SE24 9JF UK. |
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Abstract: | When parsley 2Fe-2S] and 24Fe-4S] proteins in the normal oxidised state are reduced 1:1 with Cr(II) (15-aneN4) (H2O)22+ the Cr(III) product remains attached to the protein and reduction is by an inner-sphere mechanism. With high potential 4Fe-4S] protein and rubredoxin the Cr(III) product is not attached to the protein and the mechanism is outer-sphere. Results are discussed in the context of protein crystallographic information. The Cr(III) product is not attached to the Fe2S2 core (extrusion experiments) or to the cysteinyl S-atoms (ESR). Negative patches close to the active site remain possible alternatives. |
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