Half-sandwich iron complexes bearing vinyl-selenocarboxylato ligands

Abstract

Vinyl selenocarboxylato iron complexes of the formula CpFe(CO)2SeCOCH=C(R1)(R2) {R1 = H, R2 = Me, R1 = R2 = Me, R1 = H, R2 = CH=CHMe} are synthesized by the reaction of (µ-Se)[CpFe(CO)2]2 with the corresponding vinyl acid chlorides ClCOCH=C(R1)(R2). Photolytic substitutions of CpFe(CO)2SeCOCH=CMe2 with EPh3 gave the monosubstituted complexes CpFe(CO)(EPh3)SeCOCH=CMe2 (E = P, As, Sb) in good yields. The new complexes have been characterized by UV-Vis, IR, 1H-NMR, 13C{1H}-NMR, 77Se{1H}-NMR, 31P{1H}-NMR spectroscopy and elemental analysis. The solid state structures of CpFe(CO)2SeCOCH=CMe2 and CpFe(CO)(AsPh3)SeCOCH=CMe2 were determined by X-ray crystallography. The cyclic voltammetric measurements of CpFe(CO)2SeCOCH=CMe2 were recorded. Vinyl selenocarboxylato iron complexes of the formula CpFe(CO)2SeCOCH=C(R1)(R2) {R1 = H, R2 = Me, R1 = R2 = Me, R1 = H, R2 = CH=CHMe} are synthesized by the reaction of (µ-Se)[CpFe(CO)2]2 with the corresponding vinyl acid chlorides ClCOCH=C(R1)(R2). Photolytic substitutions of CpFe(CO)2SeCOCH=CMe2 with EPh3 gave the monosubstituted complexes CpFe(CO)(EPh3)SeCOCH=CMe2 (E = P, As, Sb) in good yields. The new complexes have been characterized by UV-Vis, IR, 1H-NMR, 13C{1H}-NMR, 77Se{1H}-NMR, 31P{1H}-NMR spectroscopy and elemental analysis. The solid-state structures of CpFe(CO)2SeCOCH=CMe2 and CpFe(CO)(AsPh3)SeCOCH=CMe2 were determined by X-ray crystallography and the cyclic voltammetric measurements of CpFe(CO)2SeCOCH=CMe2 were recorded.