Bis(phthalocyaninato)niobium(IV) has been prepared and isolated as a monosolvate, [Pc2Nb]-ClNP (ClNP = 1-chloronaphthalene). It is a light-brown, stable-to-air Nb(IV) (d1) paramagnetic sandwich-like species, which, upon oxidation by I2 under mild conditions, undergoes a metal-centered monoelectronic oxidation to give the diamagnetic Nb(V) (d0) [Pc2Nb]+ fragment, with formation of saltlike species of formula [Pc2Nb](I3)(I2)0.5-(ClNP)3.5 (I). The structure of I has been elucidated by single-crystal X-ray work. Crystals are triclinic: formula C64H32N16Nb·I 3·0.5I2·3.5C10H7Cl, M = 2194.8. a = 17.702(3) Å, b = 18.708(3) Å, c = 13.504(2) Å. V= 4267.5-(13) Å3, α= 106.00(2)°, β= 93.39(2)°, γ = 83.26(1)°, Z = 2, space group P1̄. The structure of the [Pc2Nb]+ fragment, "stapled" by two inter-ligand C-C σ bonds (C11A-C11B and C31A-C31B = 1.574(15) Å), together with its color and UV-visible spectral behavior, allows a straightforward assignment of the same "stapled" structure to the unoxidized [Pc2Nb]. The present niobium sandwiched materials reiterate the peculiar structural findings shown only by the previously reported [Pc2Ti].
One Step Forward to "Stapled" Bis(phthalocyanine) Metal Complexes: Synthesis, Characterization, and Redox Properties of Bis(phthalocyaninato)niobium(IV). X-ray Crystal Structure of the Monoelectronically Oxidized Species [Pc2Nb](I3)(I2)0.5(ClNP) 3.5 (ClNP = 1-Chloronaphthalene) / Donzello, Maria Pia; Ercolani, Claudio; Angiola Chiesi, Villa; Corrado, Rizzoli. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 37:6(1998), pp. 1347-1351. [10.1021/ic970841f]
One Step Forward to "Stapled" Bis(phthalocyanine) Metal Complexes: Synthesis, Characterization, and Redox Properties of Bis(phthalocyaninato)niobium(IV). X-ray Crystal Structure of the Monoelectronically Oxidized Species [Pc2Nb](I3)(I2)0.5(ClNP) 3.5 (ClNP = 1-Chloronaphthalene)
DONZELLO, Maria Pia;ERCOLANI, Claudio;
1998
Abstract
Bis(phthalocyaninato)niobium(IV) has been prepared and isolated as a monosolvate, [Pc2Nb]-ClNP (ClNP = 1-chloronaphthalene). It is a light-brown, stable-to-air Nb(IV) (d1) paramagnetic sandwich-like species, which, upon oxidation by I2 under mild conditions, undergoes a metal-centered monoelectronic oxidation to give the diamagnetic Nb(V) (d0) [Pc2Nb]+ fragment, with formation of saltlike species of formula [Pc2Nb](I3)(I2)0.5-(ClNP)3.5 (I). The structure of I has been elucidated by single-crystal X-ray work. Crystals are triclinic: formula C64H32N16Nb·I 3·0.5I2·3.5C10H7Cl, M = 2194.8. a = 17.702(3) Å, b = 18.708(3) Å, c = 13.504(2) Å. V= 4267.5-(13) Å3, α= 106.00(2)°, β= 93.39(2)°, γ = 83.26(1)°, Z = 2, space group P1̄. The structure of the [Pc2Nb]+ fragment, "stapled" by two inter-ligand C-C σ bonds (C11A-C11B and C31A-C31B = 1.574(15) Å), together with its color and UV-visible spectral behavior, allows a straightforward assignment of the same "stapled" structure to the unoxidized [Pc2Nb]. The present niobium sandwiched materials reiterate the peculiar structural findings shown only by the previously reported [Pc2Ti].I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
