SYNTHESIS OF EARLY TRANSITION-METAL PORPHYRIN HALIDE-COMPLEXES - FIRST STRUCTURAL CHARACTERIZATION OF A VANADIUM(III) PORPHYRIN COMPLEX

A general method for the preparation of early transition metal porphyr in halide complexes using a porphyrin dianion, (THF)(2)Li-2(POR) (POR= OEP, TTP;OEP=octaethylporphyrinato, TTP=meso-tetra-p-tolylporphyrinato ), and the appropriate metal halide complex, MX(n) (MX(n) VCl3(THF)(3) , TiCl4(THF)(2), TiCl3(THF)(3), MoCl4(CH3CN)(2), WCl4), is described. The structure of (TTP)(VCl)-Cl-III.THF (2.THF) has been determined by single-crystal X-ray diffraction analysis. Complex 2.THF crystallizes in the centrosymmetric space group P2(1)/m with alpha=11.968(2) Angstr om, b=17.072(3) Angstrom, c=12.649(2) Angstrom, beta=98.62(2)degrees, V=2555.2(8) Angstrom(3), Z=2, R=4.6%, and R(w)=6.7%. The V-Cl bond len gth is 2.272(1) Angstrom, the V-N bond lengths range from 2.040(4) to 2.050(3) Angstrom, and the V-O bond distance is 2.141(3) Angstrom .