Synthesis and characterization of a series of trans->2M' (M = Mo; X = NH or M = Cr, W; X = CH2; M' = Ni, Cu, Zn) complexes and the X-ray crystal structure of trans->2Cu

Article abstract of DOI:10.1016/0022-328X(90)85449-9

A series of heterotrinuclear complexes of the type trans-<(CO)5M->2M' (M = Mo; X = NH; M' = Ni, Cu or M = Cr, W; X = CH2; 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 = CH2).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>2M' (R2 = OCH2CMe2CH2O, Ph2; M' = Ni, Cu) complexes.These studies also indicate that the coordination geometries of Ni²⁺ and Zn²⁺ in these complexes are different.The Ni²⁺ ion is in a square planar coordination environment while the coordination geometry of the Zn²⁺ is most likely tetrahedral.The molecular structure of trans-<(CO)5Mo>2Cu has been determined.The complex crystallizes from a THF-methanol mixture in the triclinic space group P1<*> (crystal data: a 6.613(2), 9.725(4), c 18.725(7) Angstroem; α 93.65(3), β 99.07(4), γ 102.85(4); Z = 1).The Cu²⁺ 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.