Synthesis and reactivity of [Re(ClCH 2Cl)(CO) 3L][A] and [Re(OSO 2CF 3)(CO) 3L] (L=Ph 2PO(CH 2) 2OPPh 2; A=BF 4, [B{3,5-(CF 3) 2C 6H 3} 4]): the crystal structure of [Re(OSO 2CF 3)(CO) 3L] and [Re(NCCH 3)(CO) 3L][BF 4

Abstract

The previously reported complex [ReBr(CO) 3L] (L=1,2-bis[diphenylphosphinite]ethane) was reacted with AgBF 4 in dichloromethane to yield fac-[Re(ClCH 2Cl)(CO) 3L][BF 4] ( 1). By contrast, reaction of the same starting material with AgOTf (OTf=OSO 2CF 3) afforded the neutral complex fac-[Re(OTf)(CO) 3L] ( 2). When 2 was treated with NaBAr F (BAr F=[B{3,5-(CF 3) 2C 6H 3} 4]) in the same solvent, the complex fac-[Re(ClCH 2Cl)(CO) 3L][BAr F] ( 3) was formed. Substitution of the loosely held ligand CH 2Cl 2 in 1 and 3 resulted in the formation of compounds of the type [Re(X)(CO) 3L][A] (X=H 2O, CH 3CN; A=BF 4 −, BAr F −), whereas the removal of OTf in 2 only was possible to form [Re(NCCH 3)(CO) 3L][OTf]. All the new complexes were characterized by 1H, 13C{ 1H}, 31P{ 1H} and 19F{ 1H} NMR as well as by IR spectroscopies. In the case of compounds 2 and [Re(NCCH 3)(CO) 3L][BF 4], 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 CH 3CN.