摘要
A new pentacoordinated ferrous compound [TPAFeCl]+ (TPA = tris(2-pyridylmethyl)amine) was synthesized from the reaction between H3TPA(ClO4)3 and Fe(PnPr3)2Cl2 in MeCN. The unique trigonal bipyramidal [TPAFeCl]+ complex was characterized as a S = 2 high spin complex based on the crystallographic structure, magnetic susceptibility, 1H NMR spectrum and semi-empirical ZINDO/S calculations. Crystal of [TPAFeCl]2(FeCl4)(MeCN)2 was monoclinic with a = 12.019(2) Å, b = 27.550(5) Å, c = 14.138(2) Å, β = 94.168(3)°, V = 4668.9(13) Å3, space group C/c, and the unit cell contained a racemic mixture of Δ and Λ isomers with ferrous tetrachloride anion.