Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel

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
methylcobalt(II) complexes. These complexes are thermally stable, and 1H 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(I) 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.