A series of divalent late transition metal complexes stabilized by diphosphine ligands such as 2,6-bis(di-t-butylphosphinomethyl)pyridine (PNP) and 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos) were synthesized and characterized by multinuclear NMR and IR spectroscopies, and in some cases by X-ray crystallography. The isostructural chloro- complexes, [M(PNP)Cl]Cl (M= Ni, Pd, Pt) and carbonyl-complexes [M(PNP)CO]Cl (M= Ir, Rh, Pt) were prepared and fully characterized. Reduction of the chloro-complexes yielded the corresponding monohydride complexes [M(PNP)H]BPh4 (M= Ni, Pd, Pt) upon precipitation with sodium tetraphenylborate. Reduction of the xantphos complexes, [M(xantphos)Cl2] under carbon monoxide yielded mononuclear dicarbonyl complexes formulated as [M(xantphos)(CO)2]. Meanwhile, the formation of a novel bridging PNP complex, Ni2(μ-PNP)(CO)6 was crystallographically established when the reduction of [Ni(PNP)Cl]Cl was carried out under a CO atmosphere.

Synthesis, characterization and reactivity of late transition metal complexes stabilized by bi- and tridentate ligands

251st National Meeting (2016)

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