Electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel

被引:208
作者
Holland, PL
Cundari, TR
Perez, LL
Eckert, NA
Lachicotte, RJ
机构
[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA
[2] Univ Memphis, Dept Chem, Memphis, TN 38152 USA
[3] Univ Memphis, Computat Res Mat Inst, Memphis, TN 38152 USA
关键词
D O I
10.1021/ja025583m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
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页码:14416 / 14424
页数:9
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