SYNTHESIS AND AXIAL LIGAND SUBSTITUTION CHEMISTRY OF RU(TTP)(NO)X - STRUCTURES OF RU(TTP)(NO)X (X = ONO, OH)

New complexes of the family Ru(TTP)(NO)X, where TTP = tetra-p-tolylpor phyrinato dianion, and X = OMe, Cl, OH, SH, S-p-tolyl, O2CH, ONO, ONO2 , N-3, or NCS, have been prepared by a variety of high-yield metathesi s techniques from Ru(TTP)(CO)(MeOH). New complexes have been character ized by IR, NMR, and UV spectroscopies as well as by cyclic voltammetr y, elemental analysis, and, in two cases, by X-ray crystallography. Th e two complexes which have been characterized by single-crystal X-ray diffraction, the hydroxide and nitrite complexes 6 and 10 both crystal lize in the monoclinic space group P2(1)/n and have Z = 6, with two in dependent metalloporphyrins in the unit cell, one (ordered) lying on a general position and the other (disordered) with the ruthenium on an inversion center. Acid labilization of the methoxide results in facile substitution kinetics at room temperature and with the exception of t he sulfhydryl complex, L = SH, the resulting complexes are air stable and thermally robust species. For example, the formate derivative cann ot be decarboxylated thermally or photolytically to give a hydride com plex, and the azido complex does not eliminate dinitrogen under simila r conditions to give a nitrido complex.