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From [M≡N] and [M—N—E] Complexes to Models for Metal Oxidoreductases
Author(s) -
Sellmann Dieter,
Sutter Jörg
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200390150
Subject(s) - carbon monoxide dehydrogenase , chemistry , hydride , reactivity (psychology) , alkylation , hydrogenase , transition metal , nitrogenase , reagent , carbon monoxide , metal , stereochemistry , medicinal chemistry , catalysis , nitrogen , organic chemistry , medicine , alternative medicine , pathology , nitrogen fixation
Abstract The article reviews results of research that was initially aiming at complexes containing new and unusual [M—N—E] element combinations (M = transition metal, E = main group element), but soon turned into studies on model complexes for metal enzymes such as nitrogenases, hydrogenases or CO dehydrogenases, because several of the resulting [M—N—E] complexes exhibited reactions relevant to these enzymes. It could be shown that alkylation of transition metal thiolate nitride complexes gives alkylimido complexes when bulky and mild alkylation reagents, e.g. Ph 3 C + , are used. Hydride addition to [Ru(NO)(py bu S 4 )] + yielded [Ru(HNO)(py bu S 4 )], which contains a bifurcated [M—N(X, Y)] bridge. The diazene complex [μ‐N 2 H 2 {Ru(PCy 3 )(S 4 )} 2 ] undergoes H + /D + and H + /D 2 exchange reactions that enabled to rationalize the until then inexplicable ‘N 2 dependent HD formation’ catalyzed by nitrogenases. Out of a larger number of [Ni(NE)(S 3 )] complexes, the compound [Ni(NHPPr 3 )(S 3 )] proved capable to model structure and reactivity features of [NiFe] hydrogenases. The [Ni(L)(S 3 )] complexes with L = N 3 — and N(SiMe 3 ) 2 — exhibit extremely high reactivity towards CO, CO 2 and SO 2 . The reactions lead to NCO — , CN — and NSO — complexes and bear potential relevance for carbon monoxide dehydrogenase reactions.