The mechanism of oxidative addition of iodine to a dimethylplatinum(II) complex

Nabavizadeh, S. Masoud; Amini, Hashem; Rashidi, Mehdi; Pellarin, Kyle R.; McCready, Matthew S.; Cooper, Benjamin F. T.; Puddephatt, Richard J.

doi:10.1016/j.jorganchem.2012.04.017

Cited by 33 publications

(16 citation statements)

References 40 publications

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“…The proposed mechanisms for halogen oxidative addition reactions point to the formation of octahedral platinum(IV) compounds in which the new ligands are mutually trans as depicted in scheme 2. [18][19][20][21] Nevertheless, further isomerisation reactions might bring these ligands to mutually cis positions. In this study, 1 H NMR spectra carried out for compounds 3 indicated the presence of only one isomer in each case.…”

Section: Synthesis and Characterization Of The Compoundsmentioning

confidence: 99%

Luminescence studies of new [C,N,N′] cyclometallated platinum(ii) and platinum(iv) compounds

et al. 2019

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Section: Synthesis and Characterization Of The Compoundsmentioning

confidence: 99%

Luminescence studies of new [C,N,N′] cyclometallated platinum(ii) and platinum(iv) compounds

et al. 2019

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“…Based on these arguments, we suggest that the strong oxidation process we observe is oxidative addition of I2 to the initially reduced Pt center, forming a hexacoordinated Pt IV complex. [34][35][36] As a random solution mixture of 0.5-1.0 mM RuPt and reactive iodine species gives according to the Stokes-Einstein equation a diffusion time of several ns, the reactive iodine species is likely present in the RuPt solvation shell. The reduced amplitude of the difference signal (despite the strong oxidation) and the slower decay rate of the initiating species suggest additional rate-limiting processes, maybe related to I2.…”

Section: Discussionmentioning

confidence: 99%

“…A number of photochemical reactions involving the bound and the now free Iions are feasible, such as the formation of I3at the Icoordination site, or the reaction of Pt with I2 or I2in an oxidative addition process, forming a hexa-coordinated Pt complex. [34][35][36] The aim of this study on RuPt is thus to shed light on the nature of the optically dark T3 state and understand the photochemical processes at the Pt catalytic moiety.…”

Section: Introductionmentioning

confidence: 99%

Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy

et al. 2018

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Photoinduced electronic and structural changes of a hydrogen-generating supramolecular RuPt photocatalyst are studied by a combination of time-resolved photoluminescence, optical transient absorption, and X-ray absorption spectroscopy. This work uses the element specificity of X-ray techniques to focus on the interplay between the photophysical and -chemical processes and the associated time scales at the catalytic Pt moiety. We observe very fast (<30 ps) photoreduction of the Pt catalytic site, followed by an ∼600 ps step into a strongly oxidized Pt center. The latter process is likely induced by oxidative addition of reactive iodine species. The oxidized Pt species is long-lived and fully recovers to the original ground state complex on a >10 μs time scale. However, the photosensitizing Ru moiety is fully restored on a much shorter ∼300 ns time scale. This reaction scheme implies that we may withdraw two electrons from a catalyst that is activated by a single photon.

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“…25,26,30 However, the analogous intermediate [PtMe 2 (I 2 )(bipy)], formed by addition of iodine, has been detected by using low-temperature NMR spectroscopy. 59,60 The calculated bond distance O··O = 2.17 Å in [PtMe 2 (CBMP)(bipy)] is considerably longer than in the free peroxide CBMP (calculated 1.58 Å, experimental 1.48 Å) 46 but the bond is sufficiently strong to keep the carboxylate groups roughly coplanar (Fig. 6c).…”

Section: Computational Studies and Conclusionmentioning

confidence: 97%

Oxidation of dimethylplatinum(II) complexes with malonyl peroxide derivatives

et al. 2015

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The reaction of the cyclic peroxides cyclobutane malonoyl peroxide and cyclopentane malonoyl peroxide to dimethylplatinum(II) complexes with the bidentate nitrogen donor ligand 4,4=-di-t-butyl-2,2=-bipyridine (bubpy) gave a mixture of the products of cis and trans oxidative addition, [PtMe 2 {(O 2 C) 2 C(C 3 H 6 )}(bubpy)] and [PtMe 2 {(O 2 C) 2 C(C 4 H 8 )}(bubpy)], respectively. The cis isomers exist with a chelating dicarboxylate ligand, forming a six-membered ring, while the trans isomers are thought to exist as oligomers, which may react with water or solvent to give complexes containing a monodentate dicarboxylate ligand. Equilibration of the product of cis oxidative addition, cis-[PtMe 2 {(O 2 C) 2 C(C 3 H 6 )}(bubpy)], with oxalic or phthalic acid to give equilibria with the oxalate cis-[PtMe 2 (O 4 C 2 )(bubpy)] or phthalate cis-[PtMe 2 {(O 2 C) 2 C 6 H 4 }(bubpy)] derivative, respectively, indicated the expected sequence of chelate stability oxalate > cyclobutane malonate > phthalate. Résumé: La réaction de peroxydes cycliques, le peroxyde de cyclobutane malonoyle et le peroxyde de cyclopentane malonoyle, avec des complexes de diméthylplatine (II) en présence du 4,4=-di-t-butyl-2,2=-bipyridine (bubpy), ligand bidentate donneur d'azote, a formé un mélange de produits d'addition oxydante cis et trans, le [PtMe 2 {(O 2 C) 2 C(C 3 H 6 )}(bubpy)] et le [PtMe 2 {(O 2 C) 2 C(C 4 H 8 )}(bubpy)], respectivement. Les complexes avec un ligand dicarboxylate chélatant existent sous forme d'isomères cis et forment un cycle à six atomes, tandis qu'on croit que les isomères trans existent sous forme d'oligomères qui peuvent réagir avec l'eau ou un solvant pour produire des complexes comprenant un ligand dicarboxylate monodentate. L'équilibration du produit d'addition oxydante cis, le cis-[PtMe 2 {(O 2 C) 2 C(C 3 H 6 )}(bubpy)], avec l'acide oxalique ou phtalique qui se produit pour former respectivement à l'état d'équilibre les dérivés cis-[PtMe 2 (O 4 C 2 )(bubpy)] oxalate ou cis-[PtMe 2 {(O 2 C) 2 C 6 H 4 }(bubpy)] phtalate, révèle la séquence de stabilité attendue des chélates : oxalate > malonate de cyclobutane > phthalate. [Traduit par la Rédaction]

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The mechanism of oxidative addition of iodine to a dimethylplatinum(II) complex

Cited by 33 publications

References 40 publications

Luminescence studies of new [C,N,N′] cyclometallated platinum(ii) and platinum(iv) compounds

Luminescence studies of new [C,N,N′] cyclometallated platinum(ii) and platinum(iv) compounds

Shedding Light on the Nature of Photoinduced States Formed in a Hydrogen-Generating Supramolecular RuPt Photocatalyst by Ultrafast Spectroscopy

Oxidation of dimethylplatinum(II) complexes with malonyl peroxide derivatives

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