Eckert Nathan A, Bones Emily M, Lachicotte Rene J, Holland Patrick L
Department of Chemistry, University of Rochester, New York 14627, USA.
Inorg Chem. 2003 Mar 10;42(5):1720-5. doi: 10.1021/ic025986n.
Nickel(II) chloride forms a complex with tetrahydrofuran, NiCl(2)(THF)(1.5), that can be used to prepare nickel chloride complexes of a bulky beta-diketiminate ligand L(Me). L(Me)NiCl and L(Me)NiCl(2)LiTHF(2), which have tetrahedral geometries in the solid state, are in equilibrium with three-coordinate L(Me)NiCl. Thermodynamic parameters for the equilibrium between L(Me)NiCl and L(Me)NiCl are DeltaH = 51(5) kJ/mol and DeltaS = 116(11) J/(mol.K). L(Me)NiCl forms a tetrahydrofuran complex with a binding constant of 1.2(2) M(-)(1) at 21 degrees C. The chloride complexes were used to generate a three-coordinate nickel(II)-amido complex. This amido complex, L(Me)NiN(SiMe(3))(2), is compared with L(Me)MN(SiMe(3))(2) (M = Mn, Fe, Co) (Panda, A.; Stender, M.; Wright, R. J.; Olmstead, M. M.; Klavins, P.; Power, P. P. Inorg. Chem. 2002, 41, 3909-3916). Trends in the metrical parameters of the three-coordinate L(Me)M(II) amido compounds are similar to the trends in three-coordinate L(tBu)M(II) chloride compounds (Holland, P. L.; Cundari, T. R.; Perez, L. L.; Eckert, N. A.; Lachicotte, R. J. J. Am. Chem. Soc. 2002, 124, 14416-14424).
氯化镍（II）与四氢呋喃形成一种配合物NiCl₂(THF)₁.₅，该配合物可用于制备大位阻β - 二酮亚胺配体L(Me)的氯化镍配合物。固态时具有四面体几何构型的[L(Me)NiCl]₂和L(Me)NiCl₂LiTHF₂与三配位的L(Me)NiCl处于平衡状态。[L(Me)NiCl]₂与L(Me)NiCl之间平衡的热力学参数为ΔH = 51(5) kJ/mol，ΔS = 116(11) J/(mol·K)。L(Me)NiCl在21℃时形成一种结合常数为1.2(2) M⁻¹的四氢呋喃配合物。这些氯化物配合物用于生成一种三配位镍（II） - 氨基配合物。将这种氨基配合物L(Me)NiN(SiMe₃)₂与L(Me)MN(SiMe₃)₂（M = Mn、Fe、Co）进行了比较（潘达，A.；施滕德，M.；赖特，R. J.；奥姆斯特德，M. M.；克拉文斯，P.；鲍尔，P. P.《无机化学》2002年，41卷，3909 - 3916页）。三配位L(Me)M(II)氨基化合物的度量参数趋势与三配位L(tBu)M(II)氯化物化合物的趋势相似（霍兰德，P. L.；坎达里，T. R.；佩雷斯，L. L.；埃克特，N. A.；拉希科特，R. J.《美国化学会志》2002年，124卷，14416 - 14424页）。
