摘要
Reaction of L0NiBr2 with 2 equiv of NaH yielded the NiII hydride complex [(L•-)Ni(μ-H) 2Ni(L•-)] (1) (L = [(2,6-iPr2C 6H3)NC(Me)]2; L0 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)2Ni(L•-)] (2a) (DME = 1,2-dimethoxyethane), which contains a mixed-valent core [Ni(μ-H) 2Ni]+. With 2 equiv of Na a doubly reduced species [Na(DME)]2[L2-Ni(μ-H)2NiL2-] (3a) was obtained, in which each monoanion (L•-) in the precursor 1 has been reduced to L2-. By using potassium as the reducing agent, two analogous species [K(DME)4][(L•-)Ni(μ-H) 2Ni(L•-)] (2b) and [K(DME)]2[L 2-Ni(μ-H)2NiL2-] (3b) were obtained. Further treatment of 3b with 2 equiv of K led to a trinuclear complex [K(DME)(THF)]2K2[L2-Ni(μ-H) 2Ni(μ-H)2NiL2-] (4), which contains one NiII and two NiI 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- η3:η3-C7H8)Ni(L •-)] (5) and [Na(DME)]2[L2-Ni(μ- η3:η3-C6H5R)NiL 2-] (6: R = CH3; 7: R = H), were isolated. Reaction of 1 with Me3SiN3 gave the N3-bridged complex [(L•-)Ni(μ-η1-N3) 2Ni(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.
源语言 | 英语 |
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页(从-至) | 13162-13170 |
页数 | 9 |
期刊 | Inorganic Chemistry |
卷 | 51 |
期 | 24 |
DOI | |
出版状态 | 已出版 - 17 12月 2012 |
已对外发布 | 是 |