653566-63-3Relevant academic research and scientific papers
Reduction of hafnium(IV) complexes in the presence of molecular nitrogen: Attempts to form dinitrogen complexes of the heaviest group 4 element
Fryzuk, Michael D.,Corkin, James R.,Patrick, Brian O.
, p. 1376 - 1387 (2007/10/03)
The reaction of [P2N2]Li2(dioxane) 2 with HfCl4(THF)2 (where [P2N 2] = PhP(CH2SiMe2NSiMe2CH 2)2PPh) results in the formation of the hafnium dichloride complex [P2N2]HfCl2 (1). The behaviour of 1 as a potential precursor in the generation of a dinitrogen coordination complex is described. Reduction of 1 with potassium-graphite (C8K), under dinitrogen, under a variety of conditions led to a number of products, one of which is the dinuclear derivative with bridging P-phenyl groups that has the general formula {[P2N 2]Hf}2 (2). Reduction of the hafnium diiodide [P 2N2]HfI2 (3) - prepared via the reaction of 1 with excess Me3SiI - with C8K results in the formation of ([P2N2]Hf)2(μ-η2:η 2-N2) (4) as the major product of the reaction, while {[P2N2]Hf}2 (2) and [P2N 2]Hf(C7H8) (5) appear to be minor products. Reaction of 1 with 2 equiv of MeMgCl gives [P2N2]HfMe 2 (6), which, upon exposure to an atmosphere of H2, gives the hafnium tetrahydride {[P2N2]Hf }2(m-H) 4 (7).
