SYNTHESIS AND CHARACTERIZATION OF THE FIRST ORGANOMETALLIC HAFNIUM PORPHYRIN COMPLEX HF(TPP)(ME)(2) (TPP=5,10,15,20-TETRAPHENYLPORPHYRINATE) AND CRYSTAL-STRUCTURE OF ITS HYDROLYSIS PRODUCT [HF(TPP)](2)(MU-O)(MU-OH)(2)

Abstract

The first organometallic hafnium(IV) porphyrin complex Hf(TPP)(Me)(2) (TPP = 5,10,15,20-tetraphenylporphyrinate) was synthesized and characterized. The H-1 NMR spectrum of the complex suggested that the methyl groups are cis to each other. An attempt to crystallize the complex yielded the trioxygen-bridged dimer complex [Hf(TPP)](2)(mu-O)(mu-OH)(2) which was presumably formed by hydrolysis. The structure of the hydrolysis product has been determined by X-ray crystallography. The crystal structure revealed two hydroxo and one oxo groups bridging two hafnium porphyrin moieties. Crystal data for [Hf(TPP)](2)(mu-O)(mu-OH)(2): orthorhombic, space group Fdd2, a=25.476(4), b=39.361(8), c=14.848(2) Angstrom, Z=8; R=0.046 and R(w),=0.049 for 1609 independent reflections with 1>3 sigma(I).