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-tolylporphyrinato 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 metathesis techniques from Ru(TTP)(CO)(MeOH). New complexes have been characterized by IR, NMR, and UV spectroscopies as well as by cyclic voltammetry, elemental analysis, and, in two cases, by X-ray crystallography. The two complexes which have been characterized by single-crystal X-ray diffraction, the hydroxide and nitrite complexes 6 and 10 both crystallize in the monoclinic space group P2(1)/n and have Z = 6, with two independent 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 the sulfhydryl complex, L = SH, the resulting complexes are air stable and thermally robust species. For example, the formate derivative cannot be decarboxylated thermally or photolytically to give a hydride complex, and the azido complex does not eliminate dinitrogen under similar conditions to give a nitrido complex.