Mononitrosyl and trans-dinitrosyl complexes of phthalocyaninates of manganese and rhenium

Tetra(n-butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthal ocyaninato(2-)manganate, (cat)[Mn(NO)(X)pc(2-)] (X = ONO, NCO, N-3: cat = ( Bu4N)-Bu-n, PNP) is prepared from acidophthalocyaninato(2-)manganese, [Mn(X )pc(2-)], (cat)NO2 and ((Bu4N)-Bu-n)BH4 in CH2Cl2 or from nitrosylphthalocy aninato(2-)manganese. [Mn(NO)pc(2-)] and ((Bu4N)-Bu-n)X (X = ONO, NCO, N-3, NCS) at T < 120 degreesC. respectively. [Mn(NO)(X)pc(2-)](-) dissociates i n methanol. and [Mn(NO)pc2-] precipitates. Nitrito(O)phthalocyaninato(2-)ma nganese, (cat)NO2 and hydrogensulfide yield trans-di(nitrosyl)phthalocyanin ato(2-)manganate. (trans)[Mn(NO)(2)pc(2-)](-) isolated as red violet (PNP) and ((Bu4N)-Bu-n) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocy aninato(2-)manganese, [Mn(NO)(OPPh3)pc(2-)] is obtained by addition of OPPh 3 to [Mn(NO)pc(2-)] at 200 degreesC. Di(triphenylphosphane)phthalocyaninato (2-)rhenium(II) and (PNP)NO2 in CH2Cl2 or in molten (PNP)NO2 and PPh3 at 10 0 degreesC yields green blue l-di( triphenylphosphane) iminium nitrosylnitr ito(O)phthalocyaninato(2-)rhenate. (l)(PNP)[Re(NO)(ONO)pc2-]. Similarly, bu t with ((Bu4N)-Bu-n)NO2 red plates of tetra-(n-butyl) ammonium trans-di(nit rosyl)phthalocyaninato(2-)rhenate, ((Bu4N)-Bu-n)(trans)[Re(NO)(2)pc(2-)] is isolated. Addition of (PNP)Br or (PNP)PF6 to a concentrated solution of (( Bu4N)-Bu-n)(trans)[Re (NO)(2)pc(2-)] in pyridine precipitates (l)(PNP)(tran s)[Re(NO)(2)pc(2-)]. ((Bu4N)-Bu-n)(trans)[Re(NO)(2)pc(2-)] and PPh3 at 300 degreesC yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninat o(2-)rhenium, [Re(NO)(OPPh3)pc2-], that is oxidised with iodine precipitati ng nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)rhenium triiodide, [Re(NO)(OPPh3)pc(2-)]I-3. The crystal structures of (l)(PNP)[Mn(NO)(ONO)pc (2-)] (1), (l)(PNP)[Mn(NO)(NCO)pc(2-)] (2), (l)(PNP)(trans)[Mn(NO)(2)pc(2-) ] (3),l(PNP)(trans)[Re(NO)(2)pc(2-)] (4) [Mn(NO)(OPPh3)pc(2-)] (5), [Re(NO) (OPPh3)pc(2-)] (6), and [Re(NO)(OPPh3)pc(2-)]I-3. CH2Cl2 (7) have been dete rmined. The M-N(NO) distance varies between 1.623(12)Angstrom in 5 and 1.84 6(3)Angstrom in 3. The M-N-O moiety is almost linear. The UV-Vis spectra wi th the B band at ca. 14500 cm(-1) and the Q band at 30400 cm(-1) do not dep endent significantly on the axial ligand and the metal atom and its oxidati on state. N-O stretching vibrations are observed in the IR spectra between 1701 cm(-1) in 3 and 1753 cm(-1) in [Mn(NO)pc(2-)] or for the Re series bet ween 1571 cm(-1) in 4 and 1724 cm(-1) in 7. M-N(NO) stretching and M-N-O de formation vibrations are assigned in the IR spectra and resonance Raman spe ctra between 486 cm(-1) in 4 and 620 cm(-1) in 1.