
Dalton Transactions p. 137 - 143 (2004)
Update date:2022-08-04
Topics:
Chen, Chien-Hong
Chang, Yung-Su
Yang, Chien-Yeh
Chen, Tai-Nan
Lee, Chien-Ming
Liaw, Wen-Feng
A number of thermally stable iron(II)-thiolate cyanocarbonyl complexes, cis,cis-[Fe(CN)2(CO)2(CS3-S,S)]2- (1), mer-[Fe(CO)2(CN)3 (NCCH3)]- (2) mer-[Fe(CO)3(CN)(CS3 -S,S)]- (3), cis-[Fe(CO)2(CN)(S(CH2)2S (CH2)2S(CH2)2S-S,S,S)]- (4), [Fe(CO)2(CN)3Br]2- (5), mer-[Fe(CO)2(CN)3(m-SC6H4Br)]2- (6) and mer-[Fe(CO)2(CN)3(SPh)]2- (7) were isolated and characterized by IR and X-ray diffraction analysis. The extrusion of one strong σ-donor CN- ligand instead of CO from the iron(II) center of the thermally stable complexes [FeII(CO)2(CN)3Br]2- (5) containing less electron-donating bromide reflects the electron-rich character of the mononuclear [FeII(CN)2(CO)2(CS3- S,S)]2- (1) when ligated by the bidentate thiolate, and the combination of one cyanide, two carbonyls and a tridentate thiolate provides the stable complex 4 as a result of the reaction of complex 5 and chelating ligand [S(CH2)2S(CH2)2 S]2-. The preference of the sixth ligand coordinated to the unsaturated [FeII(CO)(CN)2(CS3-S,S)]2- Fe(II) center, the iron-site architecture of the bimetallic Ni-Fe active-site of [NiFe] hydrogenases, is a strong π-acceptor CO group. Scrutiny of the coordination chemistry of iron(II)-thiolate cyanocarbonyl species [FeII(CO)x(CN)y(SR)z]n- reveals that certain combinations of thiolate, cyanide and carbonyl ligands(3 ≤ y + z ≤ 4) bound to Fe(II) are stable and this could point the way to understand the reasons for Nature's choice of combinations of these ligands in hydrogenases.
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