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Diiron azadithiolates with hydrophilic phosphatriazaadamantane ligand as iron-only hydrogenase active site models: Synthesis, structure, and electrochemical study by Zhen Wang; Jianhui Liu; Chengjiang He; Shi Jiang; Björn Åkermark; Licheng Sun is a Chemistry article available to read on EtoBox.

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Three novel complexes (l-adt)[Fe 2 (CO) 5 PTA] (2-PTA), (l-adt)[Fe 2 (CO) 4 PTA 2 ] (2-PTA 2 ) and (l-adt)[Fe 2 (CO) 5 DAPTA] (2-DAPTA), where adt is SCH 2 N(CH 2 CH 2 CH 3 )CH 2 S, PTA stands for 1,3,5-triaza-7-phosphaadamantane and DAPTA is 3,7-diacetyl-1,3,7-triaza-5phosphabicyclo[3.3.1]nonane, were prepared as the models of the iron hydrogenase active site through controlled CO displacement of (l-adt)[Fe 2 (CO) 6 ] with PTA and DAPTA. The coordination configurations of 2-PTA and 2-PTA 2 were characterized by X-ray crystallography. The disubstituted diiron complex 2-PTA 2 features a basal/apical coordination mode, instead of the typical transoid basal/basal configuration. Protonation of three complexes only occurred at the bridging-N atom, rather than at the tertiary nitrogen atom on the PTA or DAPTA ligands. Electrochemical properties of the complexes were studied in acetonitrile or a mixture of acetonitrile and water in the presence of acetic acid, by cyclic voltammetry. The current sensitivity of the reduced species to acid concentration in the presence of H 2 O is greater than in the pure CH 3 CN solution.

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Author

Zhen Wang; Jianhui Liu; Chengjiang He; Shi Jiang; Björn Åkermark; Licheng Sun

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0020-1693)

Published

2007

Language

EN

Field

Chemistry (Physical Sciences)