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Title: Synthesis and reactivity of nickel hydride complexes of an α-diimine ligand.
Author: Dong Q, Zhao Y, Su Y, Su JH, Wu B, Yang XJ.
Journal: Inorg Chem; 2012 Dec 17; 51(24):13162-70. PubMed ID: 23066635.
Abstract:
Reaction of L(0)NiBr(2) with 2 equiv of NaH yielded the Ni(II) hydride complex [(L(•-))Ni(μ-H)(2)Ni(L(•-))] (1) (L = [(2,6-iPr(2)C(6)H(3))NC(Me)](2); L(0) represents the neutral ligand, L(•-) is its radical-anionic form, and L(2-) denotes the dianion) in good yield. Stepwise reduction of complex 1 led to a series of nickel hydrides. Reduction of 1 with 1 equiv of sodium metal afforded a singly reduced species [Na(DME)(3)][(L(•-))Ni(μ-H)(2)Ni(L(•-))] (2a) (DME = 1,2-dimethoxyethane), which contains a mixed-valent core [Ni(μ-H)(2)Ni](+). With 2 equiv of Na a doubly reduced species [Na(DME)](2)[L(2-)Ni(μ-H)(2)NiL(2-)] (3a) was obtained, in which each monoanion (L(•-)) in the precursor 1 has been reduced to L(2-). By using potassium as the reducing agent, two analogous species [K(DME)(4)][(L(•-))Ni(μ-H)(2)Ni(L(•-))] (2b) and [K(DME)](2)[L(2-)Ni(μ-H)(2)NiL(2-)] (3b) were obtained. Further treatment of 3b with 2 equiv of K led to a trinuclear complex [K(DME)(THF)](2)K(2)[L(2-)Ni(μ-H)(2)Ni(μ-H)(2)NiL(2-)] (4), which contains one Ni(II) and two Ni(I) centers with a triplet ground state. When 1 and 3a were warmed in toluene or benzene, respectively, three reverse-sandwich dinickel complexes, [(L(•-))Ni(μ-η(3):η(3)-C(7)H(8))Ni(L(•-))] (5) and [Na(DME)](2)[L(2-)Ni(μ-η(3):η(3)-C(6)H(5)R)NiL(2-)] (6: R = CH(3); 7: R = H), were isolated. Reaction of 1 with Me(3)SiN(3) gave the N(3)-bridged complex [(L(•-))Ni(μ-η(1)-N(3))(2)Ni(L(•-))] (8). The crystal structures of complexes 1-8 have been determined by X-ray diffraction, and their electronic structures have been fully studied by EPR/NMR spectroscopy.

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