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• W2000862079 abstract "In search of water soluble transition metal complexes with sulfur dominated coordination spheres that model key reactions of nitrogenases, the benzenedithiol derivatives ‘CO2HS2’-H2 (1) and ‘CO2Me-S2’-H2 (2) were synthesized as precursors for multidentate sulfur ligands. The template alkylation of 2 by C2H4Br2 at [Fe(CO)2] fragments yielded a mixture of two diastereomeric C2 symmetrical [Fe(CO)2(‘CO2Me-S4’)] complexes (4a and 4b), which were separated by crystallization. The hydrolysis of the mixture of the diastereomers 4a and 4b led to the isomerically pure tetradentate thioether thiol ligand ‘CO2Me-S4’-H2 (5) proving the regioselectivity of the template alkylation of the asymmetrical dithiol 2. The C1 symmetrical [Fe(‘CO2Me-S2’)2]2- anion is an intermediate of the template alkylation and was isolated as (AsPh4)2 [Fe(‘CO2Me-S2’2] (11), 4a, 5 and 11 were characterized by X-ray structural analysis. Saponification of the methyl ester groups of 5 yielded ‘CO2H-S4’-H2 (7). Treatment of 7 with FeCl2 · 4 H2O in the presence of CO and LiOMe gave a mixture of two C2 symmetrical and water soluble diastereomers of Li2[Fe(CO)2(‘CO2-S4’)] (8). Upon treatment with [RuCl2 (PPh3)3] 7 yielded isomerically pure [Ru(PPh3)2-(‘CO2H-S4’)] (9). 9 also exhibits C2 symmetry and could be reversibly deprotonated to form the water soluble complex K2[Ru(PPh3)2 (‘CO2-S4’)] (10). Treatment of (NBu4)2 (‘CO2MeS2’) with “Ru(NO)Cl3” led to isomerically pure (NBu4)[Ru(NO)(‘CO2Me-S2’)2] (12)." @default.
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• W2000862079 date "1996-05-01" @default.
• W2000862079 modified "2023-10-14" @default.
• W2000862079 title "Transition Metal Complexes with Sulfur Ligands, Part 119. Synthesis of Water Soluble Fe and Ru Complexes with Novel Multidentate Thioether Thiolate Ligands Containing Carboxylate Substituents" @default.
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• W2000862079 doi "https://doi.org/10.1002/cber.19961290507" @default.
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