TIN(IV) PORPHYRIN COMPLEXES .7. CRYSTAL-STRUCTURES OF MESO-TETRAPHENYL-PORPHYRINATOTIN(IV) DIFLUORIDE AND DINITRATE, AND THE CORRELATION OFSPECTROSCOPIC DATA WITH CORE SIZE FOR TIN(IV) PORPHYRIN COMPLEXES

The structures of the complexes [Sn(tpp)F-2] (1) and [Sn(tpp)(NO3)(2)] (2) (tpp = dianion of 5,10,15,20-tetraphenylporphyrin) have been dete rmined by single crystal X-ray diffraction. Bond lengths in complex 1 are Sn-F 1.946(5) Angstrom and Sn-N 2.056(7) and 2.071(6) Angstrom. Co mplex 2 has monodentate nitrate ligands, and bond lengths Sn-O 2.113(5 ) Angstrom and Sn-N 2.075(5) and 2.080(5) Angstrom. A comparison of bo nd length and spectroscopic data for these and other [Sn(tpp)X(2)] com plexes reveals that the core sizes of the complexes of O-bound ligands and [Sn(tpp)Cl-2] correlate well with the published Sn-119 NMR linewi dths, and with Raman shifts for the band assigned as nu(CaCb). However , the Sn-N bond lengths of 1 are significantly shorter than those pred icted by such correlations.