om049165x_si_002.cif (67.25 kB)

A New Arene-Bridged Diamidophosphine Ligand and Its Coordination Chemistry with Zirconium(IV)

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posted on 14.03.2005, 00:00 by Erin A. MacLachlan, Michael D. Fryzuk
The arene-bridged dilithium diamidophosphine ligand, [(2,4,6-Me3C6H2)NLi-2-(5-MeC6H3)]2PPh, [NPN]*Li2, was prepared from (2,4,6-Me3C6H2)(2-Br-4-MeC6H3)NH, nBuLi, and PhPCl2 in Et2O and isolated as a dioxane adduct in ∼85% yield. The solid-state structure of [NPN]*Li2(THF)2 as determined by X-ray diffraction shows both lithiums bridged by the amido nitrogens with one Li ion coordinated to the phosphine donor. The reaction of [NPN]*H2 and Zr(NMe2)4 in toluene produced [NPN]*Zr(NMe2)2 in 90% isolated yield. Addition of excess Me3SiCl to [NPN]*Zr(NMe2)2 converts it to [NPN]*ZrCl2 in high yield. The solid-state structure of [NPN]*ZrCl2 as determined by X-ray diffraction shows the Zr center is a distorted trigonal bipyramid with the phosphine and the chloride apical. The ortho-Me's on the N-mesityl moiety are inequivalent in both the Li and Zr complexes of [NPN]* by NMR spectroscopy, while in [NPN]*H2 MesN ortho-Me's appear as broad singlets. VT-NMR of [NPN]*H2 indicated that ΔGrot of MesCipso−N is approximately 15.5 ± 0.3 kcal mol-1. The thermally labile and light-sensitive zirconium dimethyl complex [NPN]*ZrMe2 was prepared from [NPN]*ZrCl2 and MeMgCl in Et2O in 80% yield.

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