COORDINATION PROPERTIES OF CONSTRAINED AMINOPHOSPHINES

Abstract
The syntheses of mono and disubstituted mononuclear carbonyls of Cr, Mo, W, Fe and Ni with the cage ligand P(NMeCH2)3CMe (2) are reported. The (OC)5CrL and (OC)4FeL complexes are also described where L = As(NMeCH2)3CMe (5). Borane adducts of the complexes of (2) are reported as well as adducts of XP(NMeCH2)3CMe where X = Se and PhN. In the complexes and the selenide the BH3 group is shown from 1H nmr spectroscopy to bind to a nitrogen in a bridging group of the ligand whereas in the phenylimide it binds to the phenylimido nitrogen. Some cis and trans Pt(2)2X2 complexes are also described. The CO stretching frequencies and force constant parameters of the complexes are shown to rise in the ligand order P(NMe2)3 < (2) < (2) · BH3 and this trend is discussed in terms of constraint and inductive effects. The 31P spectra of the compounds are rationalized and 2J31P31P couplings are obtained directly from the 31P spectra of the (2) (OC) x M·(2) · BH3· complexes since the 31P nuclei are chemically nonequivalent.

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