μ-Nitruro-bis[bromo(phtalocyaninato)fer], (BrFePc)2N

Moubaraki, B.; Benlian, D.; Baldy, A.; Pierrot, M.

doi:10.1107/s0108270188012442

Cited by 26 publications

(21 citation statements)

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“…12 They are also close to the relevant crystallographic data for the bromide adduct to the N-bridged diiron non-substituted phthalocyanine dimer 23 and the crystal structure of the [(TPP)Fe] 2 N (TPP = meso-tetrakis(ptolyl)porphyrin). 24…”

Section: Exafs Spectra and Fittingsupporting

confidence: 59%

“…The structural features of 3b determined from EXAFS data (Fig. 10) can be compared to the X-ray structure of (Br)PcFe IV -N-Fe IV Pc(Br) reported by Moubaraki et al 23 The Fe-N bond distance of the linear Fe-N-Fe fragment of 3b is longer than in unsubstituted (Br)PcFe IV -N-Fe IV Pc(Br): 1.669 A ˚vs. 1.639 A ˚, respectively.…”

Section: Discussion On the Structure Of Two L-nitrido Dimersmentioning

confidence: 77%

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Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

et al. 2009

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Mu-nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl) phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mössbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe(3.5)-N-Fe(3.5) structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe(IV)-N-Fe(IV) complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe(3.5)-N-Fe(3.5) unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 A and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 A. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by tBuOOH. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.

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Section: Exafs Spectra and Fittingsupporting

confidence: 59%

Section: Discussion On the Structure Of Two L-nitrido Dimersmentioning

confidence: 77%

Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

et al. 2009

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“…A two electron electrochemical oxidation of PcFe +3.5 -N-Fe +3.5 Pc in DMF/LiBr furnished (Br)PcFe IV -N-Fe IV Pc(Br). 11 The X-ray sructural determination showed two six coordinated iron centers with short Fe-N distances (1.639 A ˚) and a linear Br-Fe-N-Fe-Br structure. Two phthalocyanine rings are staggered by an angle of 39 • , with an in-plane location of the Fe atoms.…”

Section: Introductionmentioning

confidence: 95%

Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties

et al. 2009

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Oxidation of N-bridged diiron tetra-tert-butylphthalocyanine (FePc(t)Bu)(2)N with (t)BuOOH in halogenated solvents afforded mu-nitrido diiron (IV) phthalocyanine cation radical complexes, (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) (X = Cl, Br), as evidenced by UV-vis, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry (ESI-MS), Mössbauer, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data. Continuous introduction ESI-MS showed the initial formation of the t-butylperoxo diiron complex (t)BuOO-(FePc(t)Bu)(2)N followed by intermediate formation of a monohalogenated adduct which gave the dihalogenated complex as final stable product. Fe K-edge EXAFS analysis of (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) showed bridging N atom at a distance of 1.69(1) A. The distance between two equivalent hexacoordinated in-plane iron (IV) centers is 3.39(1) A. Fe-X bond lengths are 2.33 and 2.54 A for X = Cl and Br, respectively. The use of (Cl)PcFe(IV)-N-Fe(IV)Pc(+) (Cl) for the catalytic oxidation of organic substrates has been shown for the first time.

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“…Ru, Mn, and Re, [2][3][4] and different substituted phthalocyanines, including heteroleptic complexes. [5][6][7][8][9][10] The FeNFe fragment is quasi-linear, as determined by several crystal structures 11 and EXAFS studies, 7 hence the two macrocycles are nearly parallel. -Nitrido diiron macrocyclic complexes are widely used as catalysts, because of their capability to generate high-valent oxidizing active species.…”

Section: Introductionmentioning

confidence: 98%

Alkylthio-tetrasubstituted μ-Nitrido Diiron Phthalocyanines: Spectroelectrochemistry, Electrical Properties, and Heterojunctions for Ammonia Sensing

et al. 2020

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Alkylthio-tetrasubstituted-nitrido diiron phthalocyanines complexes are synthesized with n-butyl, iso-butyl, tert-butyl and n-hexadecyl alkyl moieties. For the first time, a spectroelectrochemical investigation of -nitrido diiron phthalocyanines is achieved at all the redox steps. The complexes are stable in all their redox states, unlike their unsubstituted analogues The interest of the present complexes is to prepare sensing devices by a solution processing method. Films are characterized by electronic absorption and Raman spectroscopies. Electrical measurements on resistors show the highly resistive behavior of these complexes, whatever the chain length. However, when combined with the lutetium bisphthalocyanine, an intrinsic semiconductor, these complexes form heterojunctions that exhibit a high sensitivity to ammonia, with a very good signal over noise ratio, at room temperature and in atmospheric conditions.

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μ-Nitruro-bis[bromo(phtalocyaninato)fer], (BrFePc)2N

Cited by 26 publications

References 1 publication

Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

Preparation and characterization of μ-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation

Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties

Alkylthio-tetrasubstituted μ-Nitrido Diiron Phthalocyanines: Spectroelectrochemistry, Electrical Properties, and Heterojunctions for Ammonia Sensing

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