53432-32-9Relevant academic research and scientific papers
Mononitrosyl and trans-dinitrosyl complexes of phthalocyaninates of manganese and rhenium
Goeldner, Melanie,Geniffke, Baerbel,Franken, Andreas,Murray, Keith S.,Homborg, Heiner
, p. 935 - 947 (2001)
Tetra(n-butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthalocyaninato(2-)manganate, (cat)[Mn(NO)(X)pc2-] (X = ONO, NCO, N3; cat = nBu4N, PNP) is prepared from acidophthalocyaninato(2-)manganese, [Mn(X)pc2-], (cat)NO2 and (nBu4N)BH4 in CH2Cl2 or from nitrosylphthalocyaninato(2-)manganese, [Mn(NO)pc2-] and (nBu4N)X (X = ONO, NCO, N3, NCS) at T 2-]- dissociates in methanol, and [Mn(NO)pc2-] precipitates. Nitrito(O)phthalocyaninato(2-)-manganese, (cat)NO2 and hydrogensulfide yield trans-di(nitrosyl)phthalocyaninato(2-)manganate, trans[Mn(NO)2pc2-]-, isolated as red violet (PNP) and (nBu4N) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)manganese, [Mn(NO)(OPPh3)pc2-] is obtained by addition of OPPh3 to [Mn(NO)pc2-] at 200°C. Di(triphenylphosphane)-phthalocyaninato(2-)rhenium(II) and (PNP)NO2 in CH2Cl2 or in molten (PNP)NO2 and PPh3 at 100°C yields green blue l-di(triphenylphosphane)iminium nitrosylnitrito(O)phthalocyaninato(2-)rhenate, l(PNP)[Re(NO)(ONO)pc2-]. Similarly, but with (nBu4N)NO2 red plates of tetra-(n-butyl)-ammonium trans-di(nitrosyl)phthalocyaninato(2-)rhenate, (nBu4N)trans[Re(NO)2pc2-] is isolated. Addition of (PNP)Br or (PNP)PF6 to a concentrated solution of (nBu4N)trans[Re-(NO)2pc 2-] in pyridine precipitates l(PNP)trans[Re(NO)2Pc2-]. (nBu4N)trans[Re(NO)2PC2-] and PPh3 at 300°C yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)-rhenium, [Re(NO)(OPPh3)pc2-], that is oxidised with iodine precipitating nitrosyl(triphenylphosphane oxide)phthalocyaninato(2-)rhenium triiodide, [Re(NO)(OPPh3)pc2-]I3. The crystal structures of l(PNP)[Mn(NO)(ONO)pc2-] (1), l(PNP)-[Mn(NO)(NCO)pc2-] (2), l(PNP)trans[Mn(NO)2pc2-] (3), l(PNP)trans[Re(NO)2pc2-] (4) [Mn(NO)(OPPh3)pc2-] (5), [Re(NO)(OPPh3)pc2-] (6), and [Re(NO)(OPPh3)pc2-]I3· CH2Cl2 (7) have been determined. The M-N(NO) distance varies between 1.623(12) A in 5 and 1.846(3) A in 3. The M-N-O moiety is almost linear. The UV-Vis spectra with the B band at ca. 14500 cm-1 and the Q band at 30400 cm-1 do not dependent significantly on the axial ligand and the metal atom and its oxidation state. N-O stretching vibrations are observed in the IR spectra between 1701 cm-1 in 3 and 1753 cm-1 in [Mn(NO)pc2-] or for the Re series between 1571 cm-1 in 4 and 1724 cm-1 in 7. M-N(NO) stretching and M-N-O deformation vibrations are assigned in the IR spectra and resonance Raman spectra between 486 cm-1 in 4 and 620 cm-1 in 1. Wiley-VCH Verlag GmbH, 2001.
Darstellung und spektroskopische Charakterisierung von Nitridophthalocyaninatomangan(V)
Grunewald, Horst,Homborg, Heiner
, p. 483 - 489 (2007/10/02)
Nitridophthalocyaninatomanganese(V), MnNPc(2-), has been prepared by oxidation of - with chlorine in the presence of excess ammonia in dichloromethane as a chemically very stable, diamagnetic microcrystalline blue powder.The band at 1053 cm-1 in the infrared and resonance Raman spectra is assigned to ν(MnN).The strong resonance enhancement of ν(MnN) coincides with an electronic transition at 461 nm assigned to (N Mn) electron transfer.The UV-VIS spectrum in 1-chloronaphthalene is compared with that of the MnNPc(2-)-H2SO4 adduct and the phthalocyanine-?-cation radical +.
