78833-34-8Relevant academic research and scientific papers
Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered on switch and for dioxygen activation
Heier, Philip,Boscher, Nicolas D.,Choquet, Patrick,Heinze, Katja
, p. 11086 - 11095 (2015/01/08)
Although synthesis and substitution reactions of chlorido chromium(III) porphyrins CrIII(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chem
Molecular structure of a μ-Oxo chromium-iron complex: Rare example of a crystallographically characterized μ-Oxo heterometallic porphyrin
Oyaizu, Kenichi,Haryono, Agus,Nishimura, Yukio,Yamamoto, Kimihisa,Tsuchida, Eishun
, p. 1781 - 1784 (2007/10/03)
The crystal structure of a μ-oxo heterometallic porphyrin [(pip)(tpp)Cr(III)[OFe(III)[(tpp)] (pip = piperidine) not only confirmed the proposed oxidation state of chromium and iron atoms, but also revealed a unique coordination environment around chromium(III), which is substantially protruded from the porphyrin plane.
Oxidation of Chromium(III) Porphyrins to their ?-Radical Cations or to Oxochromium (IV) Porphyrins
Guldi, Dirk M.,Neta, Pedatsur,Hambright, Peter
, p. 2013 - 2020 (2007/10/02)
One-electron oxidation of several chromium(III) porphyrins has been studied by steady-state and pulse radiolysis techniques under different conditions.Two types of products are observed: those exhibiting intense broad absorptions at λ >/= 600 nm, ascribed
Heterobinuclear Oxo-Bridged Complexes. III. CrIIIOMoV Compounds-Synthesis and Magnetic Properties
Elliot, Robyn L.,Kruger, Paul,Murray, Keith S.,West, Bruce O.
, p. 889 - 896 (2007/10/02)
Redox reactions between CrVO(P) (P is porphyrin dianion) and MoIVO(dtc)2 (dtc is a dithiocarbamate anion) result in the formation of two oxo-bridged CrIIIOMoIV compounds.The variation of magnetic susceptibility with temperature to 25 K shows evidence for strong antiferromagnetic coupling for the pyrrolidyldithiocarbamate complex with J = -300 cm-1.
Intermediates in the Epoxidation of Alkenes by Cytochrome P-450 Models. 3. Mechanism of Oxygen Transfer from Substituted Oxochromium(V) Porphyrins to Olefinic substrates
Garrison, J. Mark,Bruice, Thomas C.
, p. 191 - 198 (2007/10/02)
Studies were initiated with the following chromium(IV) oxo porphyrin species: chromium(IV) oxide ((TPP)Cr(IV)(O)), chromium(IV) oxide ((Me12TPP)Cr(IV)(O)), chromium(IV) oxide ((Cl8TPP)Cr(IV)(O)), chromium(IV) oxide ((F8TPP)Cr(IV)(O)), and chromium(IV) oxide ((F20TPP)Cr(IV)(O)).Cyclic voltammetric (CH2Cl2, V, SCE) 1e oxidationpotentials for the couples (Porph)Cr(IV)(O)/(Porph)Cr(V)(O)(ClO4) have been determined 12TPP)Cr(IV)(O), 0.825; (Cl8TPP)Cr(IV)(O), 0.895; (F8TPP)Cr(IV)(O), 0.975; (F20TPP)Cr(IV)(O), chemically irreversible>.Standard solutions of (TPP)Cr(V)(O)(ClO4), (Me12TPP)Cr(V)(O)(ClO4), (Cl8TPP)Cr(V)(O)(ClO4), and (F8TPP)Cr(V)(O)(ClO4) were obtained by controlled-potential bulk electrolysis of the corresponding chromium(IV) oxo porphyris, and these solutions were employed in kinetic and product studies of the oxidation of a number of alkenes (CH2Cl2 solvent; 30 deg C).Under the pseudo-first-order condition of >> , the following reactions have been show to take place: (i) (Porph)Cr(V)(O)(ClO4)+alkene --> (Porph)Cr(III)(X)+epoxide (k1); (ii) (Porph)Cr(V)(O)(ClO4)+(Porph)Cr(III)(X) (Porph)Cr(IV)(O)+(Porph)Cr(IV)(X) (k2/k3); and (iii) spontaneous conversion of (Porph)Cr(V)(O) to (Porph)Cr(IV)(O) possibly by oxidation of solvent or supporting electrolyte (k4).The reversibility (k2/k3) of (ii) must be related to the formation of two different chromium(IV) porphyrinspecies, one of which is stabilized by oxo axial ligation ((Porph)Cr(IV)(O)) and one of which is not ((Porph)Cr(IV)(X); where X=Cl(-) or ClO4(-)).This is supported by the observation that the spectrum of (Me12TPP)Cr(IV)(O) remains unchanged in CH2Cl2 solutions of norbornene.Values of the second-order rate constants (k1) for alkene epoxidations were determined by both the slopes of plots of vs the pseudo-first-order rate constants (kobsd) for disappearance of and by computer simulation of the time courses for disappearance and appearance of the species (Porph)Cr(V)(O)(ClO4), (Porph)Cr(III)(X), and (Porph)Cr(IV)(O) according to reactions (i)-(iii).The two methods provided like values of k1.Values of k1 (M-1 s-1), determined from dependence of kobsd on , for reactions with (Me12TPP)Cr(V)(O)(ClO4) are the following: 5.4x1E-2, norbornene; 8.78x1E-4, cis-cyclooctene; 6.82x1E-3, cis-stilbene; and 5.19x1E-13, cyclohexene.With (Cl8TPP)Cr(V)(O)(ClO4) the values of k1 (M-1 s-1) are 9.56x1E-1 for norbornene and 2.13x1E-2 for cis-cyclooctene.Use of computer simulation of...
Oxochromium compounds. 2. Reaction of oxygen with chromium(II) and chromium(III) porphyrins and synthesis of a μ-oxo chromium porphyrin derivative
Liston, David J.,West, Bruce O.
, p. 1568 - 1576 (2008/10/08)
The reaction of oxygen with Cr(II) porphyrin complexes in solution has been found to result in the formation of CrIVO(P) compounds when oxygen is in excess. Solid CrII(P) also react irreversibly with oxygen, and the products dissolve in toluene to form CrIVO(P). The complex (TPP)CrOCr(TPP) has been isolated from the reaction of CrO(TPP) and CrII(TPP) and shown to undergo further reaction with oxygen to give CrO(TPP). The complex shows an IR absorption at 860 cm-1, considered to indicate the presence of the CrOCr linkage, and has μeff = 1.61 μB per Cr at 300 K, indicating substantial antiferromagnetic coupling. Similar μ-oxo complex formation has been demonstrated spectroscopically between other CrO(P)/Cr(P′) combinations where P and P′ may be the same or different. (P)CrOCr(P) complexes can be detected as intermediates in the reaction of CrII(P) with oxygen when the amount of oxygen is restricted. CrIII(P)Cl also reacts with oxygen in chloroform in the presence of HCl to give intermediates that are converted to CrIVO(P) in the presence of basic alumina. A Cr-porphyrin π-cation radical is proposed as the intermediate.
Oxochromium compounds. 1. Synthesis and properties of μ-oxo chromium-iron porphyrin and phthalocyanine compounds
Liston, David J.,Kennedy, Brendan J.,Murray, Keith S.,West, Bruce O.
, p. 1561 - 1567 (2008/10/08)
The reaction between CrIVO(P) and FeII(P′) leads to the formation of μ-oxo heterobinuclear complexes (P)CrOFe(P′) where P and P′ represent dianions of porphyrins that may be the same or different. [Abbreviations for the dianions of 5,10,15,20-tetraarylporphyrins: TPP, tetraphenylporphyrin; TTP, tetra-p-tolylporphyrin; TMP, tetrakis(p-methoxyphenyl)porphyrin; TFP, tetrakis(p-fluorophenyl)porphyrin; TCP, tetrakis(p-chlorophenyl)porphyrin; TXP, tetra-3,5-xylylporphyrin; OEP, the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin; Pc, the dianion of the phthalocyanine molecule.] The complexes react with heterocyclic Lewis bases, and these coordinate to Cr only. The visible, infrared, 1H NMR, and Mo?ssbauer spectra are reported for the compounds. The variation of magnetic susceptibility with temperature down to 4.2 K is interpreted in terms of strong antiferromagnetic coupling between Cr(III) (S = 3/2) and Fe(III) (S = 5/2) centers with J values in the range -130 to -150 cm-1. Zero field splitting effects are important at low temperatures. The reaction of CrO(TPP) with FeII(Pc) forms an analogous μ-oxo complex having porphyrin and phthalocyanine groups attached to Cr(III) and Fe(III), respectively.
