Synthesis and characterization of a series of trans-[(CO) 5M{Ph 2PX(CH 2) 3NCHC 6H 4- o-O}] 2M′ (M = Mo; X = NH or M = Cr, W; X = CH 2; M′ = Ni, Cu, Zn) complexes and the X-ray crystal structure of trans-[(CO) 5MO{P(OCH 2CMe 2CH 2O)NH(CH 2) 2-NCHC 6H 4- o-O}] 2Cu

Abstract

A series of heterotrinuclear complexes of the type trans-[(CO) 5M-{Ph 2PX(CH 2) 3NCHC 6H 4- o-O}] 2M′ (M = Mo; X = NH; M′ = Ni, Cu or M = Cr, W; X = CH 2; M′ = Ni, Cu, Zn) have been synthesized either by the reactions of coordinated P-donor ligands (X = NH) or by the sequential reactions of the metals with the free ligands (X = CH 2). Spectroscopic studies of the complexes (IR, UV-VIS and multinuclear NMR) indicate that their solution conformations are quite different from those of the previously studied trans-[(CO) 5MO{R 2PNH(CH 2) 2NCHC 6-H 4- o-O}] 2M′ (R 2 = OCH 2CMe 2CH 2O, Ph 2; M′ = Ni, Cu) complexes. These studies also indicate that the coordination geometries of Ni 2+ and Zn 2+ in these complexes are different. The Ni 2+ ion is in a square planar coordination environment while the coordination geometry of the Zn 2+ is most likely tetrahedral. The molecular structure of trans-[(CO) 5Mo{P(OCH 2CMe 2CH 2O)NH(CH 2) 2-NCHC 6H 4- o-O}] 2Cu has been determined. The complex crystallizes from a THF-methanol mixture in the triclinic space group P 1 (crystal data: a 6.613(2), 9.725(4), c 18.725(7) Å; α 93.65(3), β 99.07(4), γ 102.85(4); Z = 1). The Cu 2+ is coordinated to two o-salicylaldiminate groups in a trans square planar geometry, and the Mo is coordinated to five carbonyls and a P-donor group in a distorted octahedral geometry. The conformation of the bridging group in the complex is very different from that observed in other heterotrinuclear complexes due to the lack of phenyl-bis( o-salicylaldiminato)metal stacking interactions.