668491-20-1Relevant articles and documents
General synthetic route to double-butterfly Fe/S cluster complexes via reactions of the dianions {[(μ-CO)Fe2 (CO)6]2(μ-SZS-μ)}2- with electrophiles
Song, Li-Cheng,Gong, Feng-Hua,Meng, Tao,Ge, Jian-Hua,Cui, Li-Na,Hu, Qing-Mei
, p. 823 - 831 (2008/10/09)
A simple and convenient route for the synthesis of linear and macrocyclic double-butterfly Fe/S cluster complexes has been developed, which involves a sequential reaction of Fe3-(CO)12 with the dithiol HSZSH in the presence of Et3N, followed by treatment of the intermediate [Et3NH]+ salts of dianions {[(μ-CO)Fe2(CO)6]2 (μ-SZS-μ)}2- (4) with electrophiles. For example, treatment of the [Et3NH]+ salts of dianions 4 with allyl bromide and PhSBr produces the linear complexes [(μ-CH2=CHCH2) Fe2(CO)6]2(μ-SZS-μ) (5a, Z = (CH2)4; 5b, Z = CH2(CH2 OCH2)2; 5c, Z = CH2(CH2 OCH2)3CH2) and [(μ-PhS)Fe2 (CO)6]2(μ-SZS-μ) (6a, Z = CH2 (CH2OCH2)2CH2; 6b, Z = CH2(CH2OCH2)3CH2), whereas treatment with S2Cl2 and ClSZSCl yields the macrocyclic complexes [Fe2(CO)6]2(μ-S-S-μ)(μ-SZS-μ) (7a, Z = CH2(CH2OCH2)2CH2; 7b, Z = CH2(CH2OCH2)3CH2) and [Fe2(CO)6]2(μ-SZS-μ)2 (8a, Z = CH2(CH2OCH2)2CH2; 8b, Z = CH2(CH2OCH2)3CH2), respectively. In addition, while the [Et3NH]+ salts of dianions 4 react in situ with PhNCS and SCN(CH2)4NCS to give the linear complexes [(μ-PhNHC=S)Fe2(CO)6]2(μ-SZS-μ) (9a, Z = CH2CH2OCH2CH2; 9b, Z = CH2(CH2OCH2)2CH2; 9c, Z = CH2(CH2OCH2)3CH2) and macrocyclic complexes [Fe2(CO)6]2[μ-S=CNH(CH2) 4NHC=S-μ](μ-SZS-μ) (10a, Z = (CH2)4; 10b, Z = CH2(CH2OCH2)2 CH2), the in situ reactions with PhC≡CPh and PhC≡CH afford the linear complexes [(μ-σ,π-PhCH=CPh)Fe2 (CO)6]2(μ-SZ S-μ) (11a, Z = CH2 (CH2OCH2)2CH2; 11b, Z = CH2(CH2OCH2)3CH2) and [(μ-σ,π-PhCH=CH)Fe2(CO)6]2(μ-SZS -μ) (12a, Z = (CH2)4; 12b, Z = CH2 (CH2OCH2)2CH2; 12c, Z = CH2(CH2OCH2)3CH2). The possible pathways for production of these linear and macrocyclic cluster complexes are suggested, and their structures have been characterized by elemental analysis and IR and 1H NMR spectroscopy, as well as for 5a, 7a, 8a, and 12a by X-ray diffraction analysis.