Tetravalent cerium pseudohalide complexes supported by the Klaui tripodal ligand [Co(eta(5)-C5H5){P(O)(OEt)(2)}(3)](-)

摘要

Cerium(IV) pseudohalide complexes supported by the Klaui tripodal ligand [Co(eta(5)-C5H5){P(O)(OEt)(2)}(3)](-)(L-OEt(-)) have been synthesized and structurally characterized. The treatment of [Ce-IV(L-OEt)(2)Cl-2] (1) with 2 equivalents of [AgX] in acetonitrile afforded [Ce-IV(L-OEt)(2)X-2] [X- = NCS- (2), N-3(-) (3), F- (4)]. The reaction of 1 with [AgCN] in dichloromethane at -40 degrees C led to formation of a bimetallic Ce-IV/Ag-I cyanide complex that decomposed in solution at room temperature. In the presence of BPh3, 1 reacted with [AgCN] to yield the cyanoborate complex [Ce-IV(L-OEt)(2)(NCBPh3)(2)] (6) that is stable in solution. The chlorination of [Ce-IV(L-OEt)(2)(NO3)] with PhICl2 afforded [Ce-IV(L-OEt)(2)(NO3)Cl] (7) that reacted with [AgCN] to yield the heterometallic Ce-IV/Ag-I cyanide complex [{Ce(L-OEt)(2)(NO3)}(2){mu-Ag(CN)(2)}][AgCl2] (8). The reaction of [Ce-IV(L-OEt)Cl-3] with [AgN3] afforded the tetranuclear Ce-IV oxo azido cluster [C(e)4(L-OEt)(4)(mu(4)-O)(mu(2)-O)(2)(mu(2)-N-3)(6)] (9). The structures of complexes 2, 3, 6 and 9 have been established by X-ray crystallography.