Electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel
Electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel
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DOI：
10.1021/ja025583m
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发表时间：
2002-12-04
影响因子：
15
通讯作者：
Lachicotte, RJ
中科院分区：
文献类型：
--
作者：
Holland, PL;Cundari, TR;Lachicotte, RJ
三配位有机金属配合物是罕见的，特别是与原型甲基配体。使用受阻的刚性双齿配体（L），可以产生12-电子甲基铁（II）和13-电子甲基钴（II）络合物。这些配合物是热稳定的，和H-1 NMR光谱表明，低配位数保持在溶液中。尝试创建14电子LNiCH 3，而不是导致三配位镍（I）配合物LNi（THF）。LMCH 3的单晶与新的三配位氯化物配合物LNiCl和LCoCl是同晶的。沿着最近报道的LFeCl（Smith，J.M.; Lachicotte，R.J.;荷兰，P.L.化学通信2001，1542），这些是具有末端氯化物配体的三配位铁（II）、钴（II）和镍（II）络合物的仅有实例，使得能够系统地评估配位数和金属身份对M-Cl键长的影响。电子结构计算预测的三角配合物的基态。
Three-coordinate organometallic complexes are rare, especially with the prototypical methyl ligand. Using a hindered, rigid bidentate ligand (L), it is possible to create 12-electron methyliron(II) and 13-electron m ethyl cobalt(l 1) complexes. These complexes are thermally stable, and H-1 NMR spectra suggest that the low coordination number is maintained in solution. Attempts to create the 14-electron LNiCH3 led instead to the three-coordinate nickel(l) complex LNi(THF). Single crystals of LMCH3 are isomorphous with the new three-coordinate chloride complexes LNiCl and LCoCl. Along with the recently reported LFeCl (Smith, J.M.; Lachicotte, R.J.; Holland, P. L. Chem. Commun. 2001, 1542), these are the only examples of three-coordinate iron(II), cobalt(II), and nickel(II) complexes with terminal chloride ligands, enabling the systematic evaluation of the effect of coordination number and metal identity on M-Cl bond lengths. Electronic structure calculations predict the ground states of the trigonal complexes.