Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

Kinoshita, Isamu; Wright, L. James; S, Kubo; Kimura, Kentaro; Sakata, Akio; Yano, Toshihiro; Miyamoto, Riichi; Nishioka, Takanori; Isobe, Kiyoshi

doi:10.1039/b210420m

Cited by 80 publications

(72 citation statements)

References 34 publications

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“…[11] These complexes show a highly reversible one-electron oxidation process at around + 0.1 V versus the redox potential of ferrocenium/ferrocene, 6 ), which was crystallized from CH 2 Cl 2 /cyclohexane. The crystal structure of this complex is shown in Figure 1.…”

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confidence: 99%

Diamagnetic–Paramagnetic Conversion of Tris(2‐pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral

et al. 2006

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confidence: 99%

Diamagnetic–Paramagnetic Conversion of Tris(2‐pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral

et al. 2006

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“…Nevertheless, some scientific groups managed to obtain spectroscopic characteristics of products supposed to be organocuprates. Thus, UV-Vis spectroscopy and EPR give reasons to propose that organocuprates (II) may be products of photolysis of chlorocuprates CuCl 22 4 in solutions at ambient conditions or in low temperature glasses. [14,29] Indeed, the spectra and their transformations on annealing gave evidence that two new copper-containing products formed.…”

Section: Organocuprates(ii)mentioning

confidence: 99%

“…1). Szilagyi et al [32] have shown that either BP86 or BLYP functional being hybridized to that extent reproduced spin population and gave decent electronic transition energies and geometries of CuCl 22 4 . Hybrid functional named B(38HF)P86 [32] as a result gives CuACl bond lengths closer for the experimental ones than both B3LYP and BHandHLYP.…”

Section: Organocuprates(ii)mentioning

confidence: 99%

“…Over the last years organometallic chemistry of Cu(I) and Cu(III) was vastly in progress [15,16] in contrast to Cu(II); only few stable organocuprates (II) are known to date. [17][18][19][20][21][22][23][24] Meanwhile, due to spectral data not a few labile transients, probably compounds with Cu(II)AC bond, may form in conditions of catalytic and photochemical reactions or directly by reaction of Cu(I) complexes with organic radicals. [25,26] However, the interpretation of the spectra (first of all, UV-Vis, EPR-Electron Paramagnetic Resonance) is complicated and sometimes impracticable due to the absence of analogues among corresponding well-known substances.…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemistry of organocuprates as intermediates of catalytic and photochemical reactions

Голубева

Gromov

Zhidomirov

et al. 2015

Int J of Quantum Chemistry

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Organocuprates (II) and (III) are intermediates of catalytic and photochemical reactions; nevertheless, in many cases their structure and reaction ability are unclear. Quantum-chemical calculations performed within the framework of density functional theory allowed to confirm some experimental evidences of existence of such organometallic compounds. In this article, composition and geometry of organocopper transients were estimated via comparing of experimental and calculated energies of electronic transitions and g-tensors. The formation of r-bond CuAC(sp 3 ) in adducts of Cu(I) and Cu(II) complexes with alkyl-type radicals was corroborated by Natural Bonding Orbital analysis. The nuclearity of Cu(II) chloride complexes influences the mechanism of their interaction with alkyl radicals.

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“…Kinoshita (&) Á H. Hashimoto Á T. Nishioka Á R. Miyamoto Á N. Kuwamura Á Y. Yoshida Graduate School of Science, Osaka-City University, Osaka 558-8585, Japan e-mail: isamu@sci.osaka-cu.ac.jp and inexpensive catalyst, suitable for PCET, is required. We have recently investigated copper(II) complexes and found that, with the aid of strong hydrogen bonds, they can undergo PCET (Kinoshita et al 2003). The complex trispyridylthiomethylcopper(II) with axial halogen anion, for example, can be oxidized to produce corresponding copper(III) ([Cu(tptm)X]) reversibly (Miyamoto et al 2005a, b;Santo et al 2006).…”

Section: Introductionmentioning

confidence: 97%

Mimicking the photosynthetic system with strong hydrogen bonds to promote proton electron concerted reactions

et al. 2007

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A Copper(2+) complex with a Cu(II)-C bond containing sp(3) configuration was used to investigate the role of strong hydrogen bonds in proton coupled electron transfer (PCET) reactions. The only example of a Cu(II)-C system realized so far is that using tris-(pyridylthio)methyl (tptm) as a tetradentate tripodal ligand. Using this ligand, [CuF(tptm)] and [Cu(tptm)(OH)] have been prepared. The former complex forms supra-molecular arrays of layers of the complex between which hydroquinone is intercalated in the crystalline phase. This hydroquinone intercalation crystal was prepared via the photochemical conversion of quinone during the crystallization process. This conversion reaction probably involves a proton coupled electron transfer process. The nuclear magnetic resonance spectroscopic analysis of the reaction mixture shows the presence of Cu(III) during the conversion reaction. These results strongly suggest the presence of the molecular aggregate of the [CuF(tptm)] complex, water and quinone in the solution phase during the quinone to hydroquinone conversion. The presence of this type of aggregate requires a strong hydrogen bond between the [CuF(tptm)] complex and water. The presence of this particular hydrogen bond is a unique character of such a complex that has the Cu(II)-C bond. This complex is used as a model for photosynthetic water splitting since the photoconversion of quinone to hydroquinone also involves the production of oxygen from water.

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Design and synthesis of copper complexes of novel ligands based on the pyridine thiolate group

Cited by 80 publications

References 34 publications

Diamagnetic–Paramagnetic Conversion of Tris(2‐pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral

Diamagnetic–Paramagnetic Conversion of Tris(2‐pyridylthio)methylcopper(III) through a Structural Change from Trigonal Bipyramidal to Octahedral

Quantum chemistry of organocuprates as intermediates of catalytic and photochemical reactions

Mimicking the photosynthetic system with strong hydrogen bonds to promote proton electron concerted reactions

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