Unusual metalloporphycenes. First syntheses of carbonyl- and dioxo-containing osmium and ruthenium tetrapropylporphycene complexes

Li, Zao Ying; Huang, Jie; Ming, Chi; Chang, C. K.

doi:10.1021/ic00038a070

Cited by 28 publications

(4 citation statements)

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“…Insertion of ruthenium into the porphycene skeleton was achieved for 13 , , 19 , 200 – 202 (Scheme ), 224 (Scheme ), and 233 (Scheme , below). Upon irradiation of benzene solutions containing pyridine, ruthenium(II) carbonyl complexes of 13 and 19 undergo photosubstitution and yield bis-pyridine complexes. , The process is faster in porphycenes than in the corresponding 2,3,7,8,12,13,17,18-octaethylporphyrin analogue.…”

Section: Electronic Spectroscopymentioning

confidence: 99%

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Spectroscopy and Tautomerization Studies of Porphycenes

2016

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Tautomerization in porphycenes, constitutional isomers of porphyrins, is strongly entangled with spectral and photophysical parameters. The intramolecular double hydrogen transfer occurring in the ground and electronically excited states leads to uncommon spectroscopic characteristics, such as depolarized emission, viscosity-dependent radiationless depopulation, and vibrational-mode-specific tunneling splittings. This review starts with documentation of the electronic spectra of porphycenes: Absorption and magnetic circular dichroism are discussed, together with their analysis based on the perimeter model. Next, photophysical characteristics are presented, setting the stage for the final part, which discusses the developments in research on tautomerism. Porphycenes have been studied in different experimental regimes: molecules in condensed phases, isolated in supersonic jets and helium nanodroplets, and, recently also on the level of single molecules investigated by optical and scanning probe microscopies. Because of the rich and detailed information obtained from these diverse investigations, porphycenes emerge as very good models for studying the complex, multidimensional phenomena involved in the process of intramolecular double hydrogen transfer.

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Section: Electronic Spectroscopymentioning

confidence: 99%

“…Other less frequently studied metalloporphycenes are those containing rhenium ( 231 and 232 , Scheme ), osmium ( 234 and 235 , Scheme ), indium ( 223 , Scheme ), platinum ( 13 ), , molybdenum ( 19 ), and magnesium ( 19 ) …”

Section: Electronic Spectroscopymentioning

confidence: 99%

Spectroscopy and Tautomerization Studies of Porphycenes

2016

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“…1) used in this work were prepared by literature methods. 15,16 Refluxing [Ru 3 (CO) 12 ] with H 2 P* in decalin for 8 h gave [Ru(P*)(CO)] in a 90% yield, which was recrystallised from a CH 2 Cl 2 -EtOH mixture to give [Ru(P*)(CO)(EtOH)]. Its structure determined by a X-ray crystal analysis features one of the few structures of chiral ruthenium porphyrins.…”

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Catalytic and asymmetric cyclopropanation of styrenes catalysed by ruthenium porphyrin and porphycene complexes

Lo¹,

Che²,

Cheng³

et al. 1997

Chem. Commun.

124

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“…Previously, some similarities between metalloporphycenes and the corresponding metalloporphyrins have been established. ,, In the field of iron(III) porphycene chemistry, the following complexes have been characterized: (TPrPc)Fe III X (X = Cl - , Br - , N 3 - , CH 3 COO - , CF 3 COO - , C 6 H 5 O - ), , [(TPrPc)Fe III )] 2 O, , and (TPrPc)Fe III R, where TPrPc = 2,7,12,17-tetrapropylporphycene and R = aryl ligands. , By the use of electrochemistry and spectroelectrochemistry, it has been demonstrated that porphycene stabilizes high oxidation states of iron in the following systems: [(TPrPc)Fe III ] 2+ , [(TPrPc)Fe IV R] + , and {[(TPrPc)Fe IV ] 2 O} 2+ . , As shown by the formation of the interesting complex (TPrPc)Os VI (O) 2 , porphycene coordination allows for the osmium ion to be stabilized in the formal oxidation state VI . Iron(II) porphycene, when generated electrochemically, also reacts spontaneously with dioxygen to give a μ-oxo-bridged diiron(III) species (eq 1) …”

Section: Introductionmentioning

confidence: 99%

Peroxo and Ferryl Intermediates Detected by ¹H NMR Spectroscopy during the Oxygenation of Iron(II) Porphycene

2000

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The iron(III) 2,7,12,17-tetra-n-propylporphycene (TPrPc)FeIIICl is reduced using aqueous sodium dithionite or zinc amalgam to produce (TPrPc)FeII. The 1H NMR spectrum of (TPrPc)FeII (293 K; delta (ppm): pyrrole, -37.52; meso, 71.56; alpha-CH2, 27.47; beta-CH2, 8.92; gamma-CH3, 5.55) can be accounted for by the planar unligated iron(II) porphycene with an S = 1 ground electronic state. Introduction of dioxygen into a toluene-d8 solution of (TPrPc)FeII at 203 K results in the formation of the (mu-peroxo)diiron(III) porphycene (TPrPc)FeIII-O-O-FeIII(TPrPc). The value of the chemical shift of the pyrrole resonances (17.99 ppm at 203 K) of this species and its distinct non-Curie behavior imply strong antiferromagnetic iron(III)-iron(III) coupling via a mu-peroxo bridge. The (TPrPc)FeIII-O-O-FeIII(TPrPc) intermediate is stable at 203 K, but it converts into the (mu-oxo)diiron complex (TPrPc)FeIII-O-FeIII(TPrPc) upon warming above 203 K. Reaction of (TPrPc)FeIII-O-O-FeIII(TPrPc) with a nitrogen bases (B: pyridine-d5, 1-methylimidazole) results in a homolytic cleavage of the mu-peroxo bridge to form the ferryl porphycene complex B(TPrPc)FeIVO (1H NMR (223 K), delta (ppm): pyrrole, -1.32; meso, 11.80). B(TPrPc)FeIVO reacts with triphenylphosphine at 223 K to yield triphenylphosphine oxide.

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Unusual metalloporphycenes. First syntheses of carbonyl- and dioxo-containing osmium and ruthenium tetrapropylporphycene complexes

Cited by 28 publications

References 2 publications

Spectroscopy and Tautomerization Studies of Porphycenes

Spectroscopy and Tautomerization Studies of Porphycenes

Catalytic and asymmetric cyclopropanation of styrenes catalysed by ruthenium porphyrin and porphycene complexes

Peroxo and Ferryl Intermediates Detected by ¹H NMR Spectroscopy during the Oxygenation of Iron(II) Porphycene

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Unusual metalloporphycenes. First syntheses of carbonyl- and dioxo-containing osmium and ruthenium tetrapropylporphycene complexes

Cited by 28 publications

References 2 publications

Spectroscopy and Tautomerization Studies of Porphycenes

Spectroscopy and Tautomerization Studies of Porphycenes

Catalytic and asymmetric cyclopropanation of styrenes catalysed by ruthenium porphyrin and porphycene complexes

Peroxo and Ferryl Intermediates Detected by 1H NMR Spectroscopy during the Oxygenation of Iron(II) Porphycene

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Peroxo and Ferryl Intermediates Detected by ¹H NMR Spectroscopy during the Oxygenation of Iron(II) Porphycene