Nickel(II) Dihydrogen and Hydride Complexes as the Intermediates of H2 Heterolytic Splitting by Nickel Diazadiphosphacyclooctane Complexesстатья
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Аннотация:The interaction of a series of [Ni(P R1 2 N R2 2 ) 2 ] 2+ complexes 1-4 (where P R1 2 N R2 2 = 1,5-R 2 -3,7-R 1 -1,5-diaza-3,7-diphosphacyclooctane; R 1 = o‑ Py, Ph; R 2 = CHPh 2 , p- Tol) with H 2 is reversible yielding the products of heterolytic splitting of dihydrogen in the metal coordination sphere - [NiH(P R1 2 N R2 2 )(P R1 2 N R2 2 H)] 2+ . Experiments conducted with parahydrogen allowed to see the signal at about -4 ppm corresponding to the metal-bound H 2 in the nickel dihydrogen complex [Ni(η 2 -H 2 )(P Ph 2 N CHPh2 2 ) 2 ] 2+ ( 3-H 2 ) – the short-living non-classical intermediate, which so far has been revealed only computationally