Synthesis and Reactivity of Nickel Hydride Complexes of an alpha-Diimine Ligand

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	Synthesis and Reactivity of Nickel Hydride Complexes of an alpha-Diimine Ligand
	Dong QS(董青松)1,3; Zhao YX(赵艳霞)1,3; Su YT(苏远停)1,3; Su JH(苏吉虎)2; Wu B(吴彪)1; Yang XJ(杨晓娟)1
刊名	Inorganic Chemistry
	2012
卷号	51 期号:24 页码:13162-13170
ISSN号	0020-1669
通讯作者	杨晓娟
英文摘要	Reaction of L⁰NiBr₂ with 2 equiv of NaH yielded the Ni^II hydride complex [(L^•–)Ni(μ-H)₂Ni(L^•–)] (1) (L = [(2,6-iPr₂C₆H₃)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[L^2–Ni(μ-H)₂NiL^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)₂Ni(L^•–)] (2b) and [K(DME)]₂[L^2–Ni(μ-H)₂NiL^2–] (3b) were obtained. Further treatment of 3b with 2 equiv of K led to a trinuclear complex [K(DME)(THF)]₂K₂[L^2–Ni(μ-H)₂Ni(μ-H)₂NiL^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-η³:η³-C₇H₈)Ni(L^•–)] (5) and [Na(DME)]₂[L^2–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.
学科主题	物理化学与绿色催化
收录类别	SCI
资助信息	the National Natural Science Foundation of China (Grant 20972169)
语种	英语
WOS记录号	WOS:000312351800014
公开日期	2013-10-11
内容类型	期刊论文
源URL	[http://210.77.64.217/handle/362003/3832]
专题	兰州化学物理研究所_OSSO国家重点实验室兰州化学物理研究所_ERC国家工程研究中心
作者单位	1.State Key Laboratory for Oxo Synthesis & Selective Oxidation, Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000, China 2.Hefei National Laboratory for Physical Sciences at Microscale and Department of Modern Physics, University of Science and Technology of China, Hefei 230026, China 3.Graduate University of Chinese Academy of Sciences, Beijing 100049, China
推荐引用方式 GB/T 7714	Dong QS,Zhao YX,Su YT,et al. Synthesis and Reactivity of Nickel Hydride Complexes of an alpha-Diimine Ligand[J]. Inorganic Chemistry,2012,51(24):13162-13170.
APA	Dong QS,Zhao YX,Su YT,Su JH,Wu B,&Yang XJ.(2012).Synthesis and Reactivity of Nickel Hydride Complexes of an alpha-Diimine Ligand.Inorganic Chemistry,51(24),13162-13170.
MLA	Dong QS,et al."Synthesis and Reactivity of Nickel Hydride Complexes of an alpha-Diimine Ligand".Inorganic Chemistry 51.24(2012):13162-13170.