SYNTHESIS AND PROPERTIES OF (ACIDO)(NITROSYL)PHTHALOCYANINATO(2-)RUTHENIUM

(Acido) (nitrosyl)phthalocyaninato(2-)ruthenium, [Ru(X)(NO)pc(2-)] (X = F, Cl, Br, I, CN, NCO, NCS, NCSe, N-3, NO2) is obtained by acidifica tion of a solution of bis(tetra(n-butyl)ammonium) bis(nitro)phthalocya ninato(2-)ruthenate(II) in tetrahydrofurane with the corresponding con e. mineral acid or aqueous ammonium salt solution. The nitrite-nitrosy l conversion is reversal in basic media. The cyclic and differential p ulse voltammograms show mainly three quasi-reversible one-electron pro cesses at 1.05, -0.65 and -1.25 V, ascribed to the first ring oxidatio n and the stepwise reduction to the complexes of type {RuNO}(7) and {R uNO}(8), respectively. The B < Q < N regions in the electronic absorpt ion spectra are still typical for the pc(2-) ligand, but are each spli t into two strong absorptions (14500/16500(B); 28000/30500(Q); 34500/3 7000 cm(-1) (N)), whose relative intensities strongly depend on the na ture of the axial ligand X. In the IR spectra is active the N-O stretc hing vibration between 1827 (X = I) and 1856 cm(-1) (F), the C-N stret ching vibration at 2178 (X=NCO), 2072 (NCS), 2066 (NCSe), 2093 cm(-1) (CN), the N-N stretching vibration of the azide ligand at 2045 cm(-1), the fundamentals of the nitrito(O) ligand at 1501, 932, and 804 cm(-1 ), and the Ru-X stretching vibration at 483 (F), 332 (Cl), 225 (Br), 1 83 (I), 395 (N-3), 364 (ONO), 403 (CN), 263 (NCS), and 231 cm(-1) (NCS e). In the resonance Raman spectra, excited in coincidence with the B region, the Ru-NO stretching vibration and the very intense Ru-N-O def ormation vibration are selectively enhanced between 580 and 618 cm(-1) , and between 556 and 585 cm(-1), respectively.