Syntheses, structural studies, photoelectron spectra and density functional theory calculations of the "pseudo" tetraphospha-metallocenes [M(eta-P2C3Bu(t)3)(2)], (M = Ni, Pd, Pt).

Syntheses and structural characterization of the complexes [M(eta-P(2)C(3)Bu(t)(3))(2)], (M = Ni, Pd, Pt) are described. The nickel compound has an 18-electron [Ni(eta(5)-P(2)C(3)Bu(t)(3))(eta(3)-P(2)C(3)Bu(t)(3))] structure, whereas the palladium and platinum compounds both have a 16-electron [M(eta(3)-P(2)C(3)Bu(t)(3))(2)] structure (M = Pd, Pt).The electronic structure is examined and discussed using both photoelectron spectroscopy and DFT calculations.

Amination of ethers using chloramine-T hydrate and a copper(I) catalyst.

Amination of C-H bonds activated by ether oxygen atoms is facile with chloramine-T as nitrene source and copper(I) chloride in acetonitrile as catalyst. For cyclic ethers the hemiaminal products are generally stable and can be isolated pure. For acyclic ethers, the hemiaminal products, as expected, fragment with elimination of alcohol to yield imines. When activation of benzylic positions is remote through a conjugated system, stable benzylamine derivatives are isolated. Mechanistic studies are consistent with concerted insertion of an electrophilic nitrenoid into the C-H bond in the rate-determining step, though in an asynchronous manner with a more activated substrate.