X-ray crystallographic structure and physical properties of the pentacoordinated [TPAFeCl]+ complex

A new pentacoordinated ferrous compound [TPAFeCl](+) (TPA = tris(2-pyridylmethyl)amine) was synthesized from the reaction between H(3)TPA(ClO4)(3) and Fe(PPr-3)(2)Cl-2 in MeCN. The unique trigonal bipyramidal [TPAFeCl](+) complex was characterized as a S = 2 high spin complex based on the crystallographic structure, magnetic susceptibility, H-1 NMR spectrum and semi-empirical ZINDO/S calculations. Crystal of [TPAFeCl](2)(FeCl4)(MeCN)(2) was monoclinic with a = 12.019(2) angstrom, b = 27.550(5) angstrom, c = 14.138(2) angstrom, beta = 94.168(3)degrees, V = 4668.9(13) angstrom(3), space group C/c, and the unit cell contained a racemic mixture of Delta and Lambda isomers with ferrous tetrachloride anion. (c) 2007 Elsevier Ltd. All rights reserved.