Synthesis and reactivity of [Re(ClCH2Cl)(CO)(3)L][A] and [Re(OSO2CF3)(CO)(3)L] (L=Ph2PO(CH2)(2)OPPh2; A=BF4, [B{3,5-(CF3)(2)C6H3}(4)])): the crystal structure of [Re(OSO2CF3)(CO)(3)L] and [Re(NCCH3)(CO)(3)L][BF4]

摘要

The previously reported complex [ReBr(CO)(3)L] (L = 1,2-bis[diphenylphosphinite]ethane) was reacted with AgBF4 in dichloromethane to yield fac-[Re(ClCH2Cl)(CO)(3)L][BF4] (1). By contrast, reaction of the same starting material with AgOTf (OTf=OSO2CF3) afforded the neutral complex fac-[Re(OTf)(CO)(3)L] (2). When 2 was treated with NaBArF (BArF=[B{3,5-(CF3)(2)C6H3}(4)]) in the same solvent, the complex fac-[Re(ClCH(2)Gl)(CO)(3)L][BArF] (3) was formed. Substitution of the loosely held ligand CH2Cl2 in 1 and 3 resulted in the formation of compounds of the type [Re(X)(CO)(3)L][A] (X = H2O, CH3CN; A = BF4- BArF), whereas the removal of OTf in 2 only was possible to form [Re(NCCH3)(CO)(3)L][OTf]. All the new complexes were characterized by H-1, C-13{H-1}, P-31{H-1} and F-19{H-1} NMR as well as by IR spectroscopies. In the case of compounds 2 and [Re(NCCH3)(CO)(3)L][BF4], X-ray suitable crystals were isolated. In both cases, the Re atom adopts six-coordination by bonding to the three CO ligands, the two P atoms of L and either the oxygen atom of the OTf anion or the N atom of CH3CN. (C) 2004 Elsevier Ltd. All rights reserved.