New coordination polymers based on the triangular [Cu3(μ3-OH)(μ-pz)3]2+ unit and unsaturated carboxylates

Contaldi, Simone; Nicola, Corrado Di; Garau, Federica; Karabach, Yauhen Yu.; Martins, Luísa M. D. R. S.; Monari, Magda; Pandolfo, Luciano; Pettinari, Cláudio; Pombeiro, Armando J. L.

doi:10.1039/b823370e

Cited by 85 publications

(71 citation statements)

References 96 publications

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“…The Fe-O bond length in 1a [1.740 Å] and 2a [1.747 Å] are similar to those of μ-oxo-diiron(III)-(porphyrinates),55 and the short Cu-O bond distances [1.856 Å in 1a and 1.815 Å in 2a ] are not far off from values observed for bis-μ-oxodicopper(III) complexes (Cu-O = 1.8 Å) 33,56. To further compare, a high-spin (heme)Fe III -hydroxide Fe-O bond lengths is 1.86 Å,57 while for example Cu II -hydroxide Cu-O(H) bond lengths in complexes with the Cu II -O(H)-Fe III (1.89-1.95 Å)50,58 or Cu II 2 (OH – ) 2 / Cu II (OH – ) core (1.9 – 2.0 Å) are greater 59-67…”

Section: Resultsmentioning

confidence: 97%

Heme−Copper−Dioxygen Complexes: Toward Understanding Ligand-Environmental Effects on the Coordination Geometry, Electronic Structure, and Reactivity

et al. 2010

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The nature of the ligand is an important aspect of controlling structure and reactivity in coordination chemistry. In connection with our study of heme/copper/oxygen reactivity relevant to cytochrome c oxidase O 2 -reduction chemistry, we compare the molecular and electronic structure of two highspin heme-peroxo-copper [Fe III -O 2 2--Cu II ] + complexes containing N 4 -tetradentate (1) or N 3 -tridentate (2) copper ligands. Combining previously reported and new resonance Raman and EXAFS data coupled to DFT calculations we report a geometric structure and more complete electronic description of the high-spin heme-peroxo-copper complexes 1 and 2, which establish μ-(O 2 2-) sideon to the Fe III and end-on to Cu II (μ-η 2 :η 1 ) binding for the complex 1 but side-on/side-on (μ-η 2 :η 2 ) μ-peroxo coordination for the complex 2. We also compare and summarize the differences and similarities of these two complexes in their reactivity toward CO, PPh 3 , acid and phenols. The comparison of a new X-ray structure of μ-oxo complex 2a with the previously reported 1a X-ray structure, two thermal decomposition products respectively of 2 and 1, reveals a considerable difference in the Fe-O-Cu angle between the two μ-oxo complexes (∠Fe-O-Cu = 178.2° in 1a, ∠Fe-O-Cu = 149.5° in 2a). The reaction of 2 with one equivalent of exogenous N-donor axial base leads to the formation of a distinctive low-temperature stable, low-spin heme-O 2 -Cu complex (2b), but under the same conditions the addition of an axial base to 1 leads to the dissociation of the hemeperoxo-Cu assembly and the release of O 2 . 2b reacts with phenols performing hydrogen-atom (e -+ H + ) abstraction resulting in O-O bond cleavage and the formation of high-valent ferryl [Fe IV =O] complex (2c). The nature of 2c was confirmed by comparison of its spectroscopic features and reactivity with those of an independently prepared ferryl complex. The phenoxyl radical generated by the hydrogen-atom abstraction was either 1) directly detected by EPR spectroscopy using phenols that produce stable radicals or 2) indirectly by detection of the coupling product of two phenoxyl radicals.karlin@jhu.edu, edward.solomon@stanford.edu. Supporting Information Available. UV-visible spectra of the reaction of (2b) with 1 equiv. of 2,4-di-tertbutylphenol ( Figure S1), UVvis spectra of the reaction of [(F 8 )Fe III -(O 2 2-)-Cu II (TMPA)] + (1) with DMAP ( Figure S2), EPR spectra of (2b) reaction with 1 equiv.of 2,4-di-tert-butylphenol ( Figure S3), GC-MS trace of the oxidative coupling of 2,4-di-tert-butylphenol in presence of (2b) ( Figure S4), ORTEP diagram ( Figure S5) and crystal data and structure refinement for [(F 8 )Fe III -(O 2-)-Cu II (AN)] + (2a) X-ray structure (Table S1), XAS spectra and computational data.NIH Public Access

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Section: Resultsmentioning

confidence: 97%

Heme−Copper−Dioxygen Complexes: Toward Understanding Ligand-Environmental Effects on the Coordination Geometry, Electronic Structure, and Reactivity

et al. 2010

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“…[54] In this case, the pyrazole ligands mediate stronger antiferromagnetic interactions than the analogous carboxylates. [56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72] Most of the trinuclear centred copper(II) triangles are synthesized from a copper(II) salt and the pyrazole ligand in a molar ratio 1:1 or 1:2, in the presence of base and with use of different counterions. [55] Numerous compounds were synthesized with the copper(II) ion.…”

Section: Polynuclear Compounds Pyrazole Ligands With Non-coordinatingmentioning

confidence: 99%

Coordination Versatility of Pyrazole‐Based Ligands towards High‐Nuclearity Transition‐Metal and Rare‐Earth Clusters

et al. 2010

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“…Thus, it is more correct to write "the A/K ratio determined after reduction of the sample with PPh 3 " [254,255]. When we have only the chromatogram obtained after the addition of PPh 3 , we cannot definitively say that ROOH is present in the reaction solution (for example, [256]).…”

Section: Detection and Determination Of Alkyl Hydroperoxides Comparinmentioning

confidence: 99%

“…Thus, it is more correct to write "the A/K ratio determined after reduction of the sample with PPh3" [254,255] …”

Section: Detection and Determination Of Alkyl Hydroperoxides Comparinmentioning

confidence: 99%

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

Shul’pin

2016

Catalysts

174

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This review describes new reactions catalyzed by recently discovered types of metal complexes and catalytic systems (catalyst + co-catalyst). Works of recent years (mainly 2010-2016) devoted to the oxygenations of saturated, aromatic hydrocarbons and other carbon-hydrogen compounds are surveyed. Both soluble metal complexes and solid metal compounds catalyze such transformations. Molecular oxygen, hydrogen peroxide, alkyl peroxides, and peroxy acids were used in these reactions as oxidants.

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New coordination polymers based on the triangular [Cu3(μ3-OH)(μ-pz)3]2+ unit and unsaturated carboxylates

Cited by 85 publications

References 96 publications

Heme−Copper−Dioxygen Complexes: Toward Understanding Ligand-Environmental Effects on the Coordination Geometry, Electronic Structure, and Reactivity

Heme−Copper−Dioxygen Complexes: Toward Understanding Ligand-Environmental Effects on the Coordination Geometry, Electronic Structure, and Reactivity

Coordination Versatility of Pyrazole‐Based Ligands towards High‐Nuclearity Transition‐Metal and Rare‐Earth Clusters

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

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