- Reactions of a gallium(ll)-diazabutadiene dimer, [(([(H)C(BU t)N]2)GaI)2], with [MESiMe3J 2] (M = Li or Na; e = N, P, or As): Structural, EPR, and ENDOR characterization of paramagnetic gallium(lll) pnictide complexes
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The reactions of the paramagnetic gallium(ll) complex [((Bu t-DAB)Gal)2] (But-DAB = {(Bu tNC(H)}2) with the alkali metal pnictides [ME(SiMe 3)2] (M = Li or Na; E = N, P, or As) have been carried out under a range of stoichiometries. The 1:2 reactions have led to a series of paramagnetic gallium(III)-pnictide complexes, [(But-DAB) Ga{E(SiMe3)2}I] (E = N, P, or As), while two of the 1:4 reactions afforded [(But-DAB)Ga{ E(SiMe3) 2}2] (E = P or As). In contrast, treatment of [{(Bu t-DAB)Gal)2] with 4 equiv of [NaN(SiMe3) 2} resulted in a novel gallium heterocycle coupling reaction and the formation of the diradical species [(But-DAB)Ga{N(SiMe 3)2){[CC(H)N2(But) 2]Ga[N(SiMe3J2]CH3)]. The mechanism of this unusual reaction has been explored, and evidence suggests it involves an intramolecular transmethylation reaction. The X-ray crystal structures of all prepared complexes are reported, and all have been characterized by EPR and ENDOR spectroscopies. The observed spin Hamiltonian parameters provide a detailed picture of the distribution of the unpaired spin density over the molecular frameworks of the complexes.
- Antcllff, Karen L.,Baker, Robert J.,Jones, Cameron,Murphy, Damien M.,Rose, Richard P.
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p. 2098 - 2105
(2008/10/09)
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