Date: November 8, 2002
Creator: Holland, Patrick L.; Cundari, Thomas R., 1964-; Perez, Lanyn L.; Eckert, Nathan A. & Lachicotte, Rene J.
Description: This article discusses electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel. Abstract: 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 lenghts. Electronic structure calculations predict the ground states of the trigonal complexes.
Contributing Partner: UNT College of Arts and Sciences