SYNTHESES AND PROPERTIES OF (ACIDO)(PYRID INE)PHTHALOCYANINATO(2-)RUTHENATES(II) - CRYSTAL-STRUCTURE OF TETRA(N-BUTYL)AMMONIUM (CYANO)(PYRIDINE)PHTHALOCYANINATO(2-)RUTHENATE(II)

Bis(tetra(n-butyl)ammonium bis(acido)phthalocyaninato(2-)ruthenate(II) reacts in boiling pyridine to yield blue purple, diamagnetic tetra(n- butyl) ammonium (acido)(pyridine)phthalocyaninato(2-)rut ((Bu4N)-Bu-n) [Ru(X)(py)pc(2-)] (X = CN, N-3, NCS, NCO, NO2). ((Bu4N)-Bu-n) [Ru(CN) (py)pc(2-)] crystallizes in the orthorhombic space group Pca2(1) (no. 29) with cell parameters a = 28.319(5) Angstrom, b = 29.850(3) Angstro m, c = 24.566(7) Angstrom, Z = 16, with four crystallographically inde pendent complex anions present in the unit cell. Each Ru atom is locat ed outside the centre (Ct) of the corresponding (N-iso)(4) plane (N-is o: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (N-iso)(4) plane towards cyanide (d(Ru-Ct)) is 0.020 Ang strom. The Ru-N-iso distance varies from 1.947(2) to 1.992(2) Angstrom . The average Ru-C and Ru-N-py distance is 2.00 Angstrom and 2.19 Angs trom, respectively. The pc(2-) ligand ist slightly distorted towards t he cyanide. The cyclic and differential pulse voltammograms of ((Bu4N) -Bu-n)[RU(X)(py)pc(2-)] exhibit the first quasi-reversible one-electro n process (in V) at 0.46 (X = CN), 0.34 (N-3), 0.40 (NCO), 0.47 (NO2), 0.50 V (NCS) and the second, independent of X, at approximately 1.05 V. The first process is metal directed, the second ring directed. The electronic absorption spectra and the vibrational spectra of ((Bu4N)-B u-n)[Ru(X)(py)pc(2-)] are discussed.