A Bridging Peroxide Complex of Platinum(IV)

Hoseini, S. Jafar; Fath, Roghayeh Hashemi; Fard, Mahmood Azizpoor; Behnia, Ava; Puddephatt, Richard J.

doi:10.1021/acs.inorgchem.8b00888

Cited by 7 publications

(6 citation statements)

References 42 publications

(33 reference statements)

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“…The formation of stable side-on peroxo M(III) complexes from the reaction of square-planar d 8 metal complexes with oxygen is well-known for group 9. − In particular, it is worth noting the iridium(III) phenyl complexes with a side-on peroxo ligand, very similar to the Pt(IV) complex seen here, that were reported by Wendt and Milstein. , For Pd(II) and Pt(II) complexes, the reaction with oxygen has resulted in a number of products (see Scheme ). In addition to side-on peroxo complexes, the formation of a Pd(III) superoxide complex has been observed, or in the presence of protic solvents, a hydroperoxo Pt(IV) complex was obtained. , The formation of a dinuclear Pt(IV) complex with two bridging peroxide ligands is also possible. , The latter has shown the IR stretch ν(OO) = 807 cm –1 for the bridging peroxide moieties . The possible formation of the bridging bis(peroxide) dinuclear complex [Pt( BPI )(μ-O 2 )Ph] 2 was considered, but the lower ν(OO) = 773 cm –1 and the MS data suggest a mononuclear [Pt( BPI )(μ-O 2 )Ph] complex.…”

Section: Resultsmentioning

confidence: 99%

“…83,84 The formation of a dinuclear Pt(IV) complex with two bridging peroxide ligands is also possible. 82,85 The latter has shown the IR stretch ν(OO) = 807 cm −1 for the bridging peroxide moieties. 85 The possible formation of the bridging bis-(peroxide) dinuclear complex [Pt(BPI)(μ-O 2 )Ph] 2 was considered, but the lower ν(OO) = 773 cm −1 and the MS data suggest a mononuclear [Pt(BPI)(μ-O 2 )Ph] complex.…”

Section: ■ Introductionmentioning

confidence: 98%

“…80,81 For Pd(II) and Pt(II) complexes, the reaction with oxygen has resulted in a number of products (see Scheme 3). 82 In addition to side-on peroxo complexes, the formation of a Pd(III) superoxide complex has been observed, 29 or in the presence of protic solvents, a hydroperoxo Pt(IV) complex was obtained. 83,84 The formation of a dinuclear Pt(IV) complex with two bridging peroxide ligands is also possible.…”

Section: ■ Introductionmentioning

confidence: 99%

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Photolytic Activation of Late-Transition-Metal–Carbon Bonds and Their Reactivity toward Oxygen

Lam

Aguirre

et al. 2021

Organometallics

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The photolytic activation of palladium(II) and platinum(II) complexes [M(BPI)(R)] (R = alkyl, aryl) featuring the 1,3-bis(2-pyridylimino)isoindole (BPI) ligand has been investigated in various solvents. In the absence of oxygen, the formation of chloro complexes [M(BPI)Cl] is observed in chlorinated solvents, most likely due to the photolytic degradation of the solvent and formation of HCl. The reactivity of the complexes toward oxygen has been studied both experimentally and computationally. Excitation by UV irradiation (365 nm) of the metal complexes [Pt(BPI)Me] and [Pd(BPI)Me] leads to distortion of the square-planar coordination geometry in the excited triplet state and a change in the electronic structure of the complexes that allows the interaction with oxygen. TD-DFT computational studies suggest that, in the case of palladium, the Pd(III) superoxide intermediate [Pd(BPI)(κ 1 -O 2 )Me] is formed and, in the case of platinum, the Pt(IV) peroxide intermediate [Pt(BPI)(κ 2 -O 2 )Me]. For alkyl complexes where metal−carbon bonds are sufficiently weak, the photoactivation leads to the insertion of oxygen into the metal−carbon bond to generate alkylperoxo complexes: for example [Pd(BPI)OOMe], which has been isolated and structurally characterized. For stronger M−C(aryl) bonds, the reaction of [Pt(BPI)Ph] with O 2 and light results in a Pt(IV) complex, tentatively assigned as the peroxo complex [Pt(BPI)(κ 2 -O 2 )Ph], which in chlorinated solvents reacts further to give [Pt(BPI)Cl 2 Ph], which has been isolated and characterized by scXRD. In addition to the facilitation of oxygen insertion reactions, UV irradiation can also affect the reactivity of other components in the reaction mixture, such as the solvent or other reaction products, which can result in further reactions. Labeling studies using [Pt(BPI)(CD 3 )] in chloroform have shown that photolytic reactions with oxygen involve degradation of the solvent.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 98%

Section: ■ Introductionmentioning

confidence: 99%

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Photolytic Activation of Late-Transition-Metal–Carbon Bonds and Their Reactivity toward Oxygen

Lam

Aguirre

et al. 2021

Organometallics

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“…The construction of multinuclear metal assemblies has been a growing area of research during the past decade. , Developments based on the use of different ligands as the building unit for the synthesis of compounds have been reported for binuclear Pt complexes, − although to the best of our knowledge, tetranuclear complexes are rare. − …”

Section: Introductionmentioning

confidence: 99%

Chelating and Bridging Roles of 2-(2-Pyridyl)benzimidazole and Bis(diphenylphosphino)acetylene in Stabilizing a Cyclic Tetranuclear Platinum(II) Complex

et al. 2019

Self Cite

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The reaction of complex [Pt(Me)(DMSO)(pbz)], 1, (pbz = 2-(2-pyridyl)benzimidazolate) with [PtMe(Cl)(DMSO)2], B, followed by addition of bis(diphenylphosphino)acetylene (dppac), gave the novel tetranuclear platinum complex [Pt4Me4(µ-dppac)2(pbz)2Cl2], 2, bearing both the pbz and dppac ligands. In this structure, the pbz ligands act as both chelating and bridging to stabilize the tetraplatinum framework. The tetranuclear Pt(II) complex was fully characterized by NMR spectroscopy, X-ray crystallography and mass spectrometry and its electronic structure was investigated and supported by DFT calculations.

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“…The state of the art of rainwater harvesting systems including their design, construction, and management has been thoroughly reviewed in 2016, [15] and excellent books have been lately published. [3,8] Referring to recent advances and findings from reallife applications around the world, this work provides an answer to several relevant questions of direct interest to policy makers and tomorrow's adopters of broadened distributed generation.…”

Section: Introductionmentioning

confidence: 99%

Expanding the Distributed Generation Concept: Toward Decentralized Energy and Water Supply

Ciriminna

Pecoraino²,

Meneguzzo

et al. 2018

Global Challenges

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Rainwater harvesting decentralizes the water supply in full analogy to what building‐integrated photovoltaics and solar thermal do for electricity and heat. In this new decentralized generation scenario, the built environment is used to collect both sunlight photons and water molecules with significant economic and environmental benefits. Referring to recent progress and to real‐life findings from around the world, this work provides an answer to several relevant questions of direct interest to policy makers and early adopters of broadened distributed generation. The conclusions offer guidelines for developing a successful distributed generation strategy at the regional level by unifying solar energy and water management policies.

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A Bridging Peroxide Complex of Platinum(IV)

Cited by 7 publications

References 42 publications

Photolytic Activation of Late-Transition-Metal–Carbon Bonds and Their Reactivity toward Oxygen

Photolytic Activation of Late-Transition-Metal–Carbon Bonds and Their Reactivity toward Oxygen

Chelating and Bridging Roles of 2-(2-Pyridyl)benzimidazole and Bis(diphenylphosphino)acetylene in Stabilizing a Cyclic Tetranuclear Platinum(II) Complex

Expanding the Distributed Generation Concept: Toward Decentralized Energy and Water Supply

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