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Oxorhenium(V) complexes with bis-phosphinite chelating coligands. The crystal structure of [ReOCl2(OMe)L1], [ReOCl3L2], [ReOCl2(OEt)L2] and [ReOCl2{Ph2PO(CH2)2O}{PPh2(OEt)}] [L1=Cy2PO(CH2)2OPCy2, L2=Ph2PO(CH2)2OPPh2]

2003; Elsevier BV; Volume: 22; Issue: 13 Linguagem: Inglês

10.1016/s0277-5387(03)00334-6

1873-3719

S. Bolaño, Jorge Bravo, Rosa Carballo, E. Freijanes, Soledad García‐Fontán, P. Rodríguez-Seoane,

Radioactive element chemistry and processing

The new ligand 1,2-bis(dicyclohexylphosphinite)ethane (L1) was prepared by reaction of ethylenglycol with dicyclohexylphosphine in the presence of triethylamine. By treating this ligand with the arsine complex [ReOCl3(AsPh3)2] and trituring the formed oil with methanol, the complex [ReOCl2(OMe)L1] (1) was isolated and its crystal structure was studied by X-ray diffractometry. The coordination sphere around the Re atom is a pseudo-octahedron. The crystal structure of the previously reported complex [ReOCl3L2] (2) (L2=1,2-bis[diphenylphosphinite]ethane) was solved by X-ray diffractometry. When Complex 2 was refluxed in EtOH, the oxo-alkoxide complex [ReOCl2(EtO)L2] (3) was formed by a metathesis reaction. X-ray diffraction studies of Complex 3 show a pseudo-octahedral geometry around the Re atom with the oxo and ethoxy groups mutually trans. Finally, reaction of 2 with the monodentate phosphinite PPh2(OEt) ligand yielded the paramagnetic Re(III) compound [ReCl3L2{PPh2(OEt)}] (previously reported) and the new unexpected Re(V) by-product [ReOCl2(Ph2POCH2CH2O){PPh2(OEt)}] (4). On the contrary, compounds 1 and 3 did not react with PPh2(OEt) under the same conditions.