Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism

Nabavizadeh, S. Masoud; Amini, Hashem; Jame, Fatemeh; Khosraviolya, Sedigheh; Shahsavari, Hamid R.; Hosseini, Fatemeh Niroomand; Rashidi, Mehdi

doi:10.1016/j.jorganchem.2011.10.028

Cited by 44 publications

(81 citation statements)

References 65 publications

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“…The known organoplatinum(II) complex [PtMe(ppy) (PMePh 2 )], 1b (reported previously [17]), was further identified by single crystal Xeray diffraction analysis (Fig. 2).…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 67%

“…2-In 31 P NMR spectra of the starting organoplatinum(II) complexes [PtMe(ppy) (P(OPh) 3 The known organoplatinum(IV) complex [PtMe 2 I(ppy) (PPh 3 )], 2a (reported previously [17]), was further identified by single crystal Xeray diffraction analysis (Fig. 3).…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 85%

“…Kinetic studies were carried out by using a PerkineElmer Lambda 25 spectrophotometer with temperature control using an EYELA NCB-3100 constant-temperature bath. The complexes [PtMe(ppy) (SMe 2 )] and [PtMe(bhq) (SMe 2 )] were prepared as described previously [17]. …”

Section: General Remarks and Synthesismentioning

confidence: 99%

“…The starting complexes [PtMe(C^N)L], 1a, 1b and 1d, in which C^N ¼ 2-phenylpyridinate (ppy) or benzo[h]quinolinate (bhq), and L ¼ PPh 3 , or PMePh 2 , were synthesized according to literature [17,18]. The new analogous complexes [PtMe(ppy) (P(OPh) 3 )], 1c, and [PtMe(bhq) (P(OPh) 3 )], 1e, were prepared similarly by the reaction of [PtMe(ppy) (SMe 2 )] or [PtMe(bhq) (SMe 2 )], respectively, with 1 equiv P(OPh) 3 .…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 99%

“…The new analogous complexes [PtMe(ppy) (P(OPh) 3 )], 1c, and [PtMe(bhq) (P(OPh) 3 )], 1e, were prepared similarly by the reaction of [PtMe(ppy) (SMe 2 )] or [PtMe(bhq) (SMe 2 )], respectively, with 1 equiv P(OPh) 3 . Either of these starting methylplatinum(II) complexes, 1ae1e, was reacted cleanly with an excess of MeI in acetone at room temperature giving a very pale yellow solution, from which the thermodynamic isomer product [PtMe 2 I(C^N)L], 2ae2e, was obtained (see Scheme 1) [17].…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 99%

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Secondary kinetic deuterium isotope effect in oxidative addition reaction of cycloplatinated(II) complexes with MeI

Hamidizadeh

Rashidi

Nabavizadeh

et al. 2015

Journal of Organometallic Chemistry

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“…The known organoplatinum(II) complex [PtMe(ppy) (PMePh 2 )], 1b (reported previously [17]), was further identified by single crystal Xeray diffraction analysis (Fig. 2).…”

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 67%

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 85%

Section: General Remarks and Synthesismentioning

confidence: 99%

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 99%

Section: Synthesis and Characterization Of The Complexesmentioning

confidence: 99%

See 3 more Smart Citations

Secondary kinetic deuterium isotope effect in oxidative addition reaction of cycloplatinated(II) complexes with MeI

Hamidizadeh

Rashidi

Nabavizadeh

et al. 2015

Journal of Organometallic Chemistry

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Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Sravani

Venkatesh

Vijayakrishna

et al. 2014

Applied Organom Chemis

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Intermediates for many catalysis reactions reported in the literature are metal‐alkyl and metal‐alkenyl, including metallacycloalkane species. Synthesis and reactions of metal‐alkyl, alkenyl and metallacyle complexes have shown a great deal of development during the past few decades. This review summarizes the significant contributions reported on metal‐alkenyl compounds, specifically those containing at least a carbon chain with pendant alkene group [M―CH2CH2CHCH2]. Although metal‐alkenyl complexes are stable with strong chelating diphosphines and with a decrease in the ligand donor strength, the complexes can decompose without any ambiguity. For example, platinum‐dialkenyl complexes react readily via β‐hydrogen elimination and reductive elimination promoted by the nature of the ligand, solvent and length of carbon chains. These complexes can also undergo intramolecular irreversible isomerization and this leads to the selective catalytic isomerization of 1‐alkenes to 2‐alkenes in the presence of platinum‐dialkenyl complexes as catalysts. Perhaps the most striking manifestations of flexibility are the facile and complete intramolecular and intermolecular alkene metathesis to yield the corresponding metallacycloalkenes in the presence of Grubbs’ catalysts. The diverse chemical reactivity of these complexes demonstrates both the scope and complexity of metal‐alkenyl chemistry depending on the nature of ligand and metal. Copyright © 2014 John Wiley & Sons, Ltd.

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Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands

Shahsavari

Aghakhanpour

Hossein-Abadi

et al. 2018

Applied Organom Chemis

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The present investigation introduces a new series of cycloplatinated(II) complexes, with the general formula Pt(O-bpy)(Me)(CN-R)] (R = benzyl, 2-naphtyl and tert-butyl), which are able to generate the stable trans-Pt(IV) product in the solution after the reaction with iodomethane. In fact, the trans product is both the kinetic and thermodynamic product of the reaction; this observation was supported by DFT calculations. These Pt(II) complexes are supported by 2,2'-bipyridine N-oxide (O-bpy) and one of several isocyanides as the cyclometalated and ancillary ligands, respectively. These new Pt(II) complexes undergo oxidative addition with MeI to give the corresponding trans-Pt(IV) complexes. All the complexes were identified employing the multi-nuclear NMR spectroscopy and single crystal X-ray crystallography. The kinetic investigations were also performed for the oxidative addition reactions in order to measure the reaction rates; the reaction was followed by UV-Vis spectroscopy. The rates obtained follow the trend CN-t Bu > CN-Bz > CN-2 Np for the CN-R ligands in the Pt(II) complexes. The order can be related to the degree of electron-donation of the R group (tert-butyl > benzyl > 2-naphtyl).

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Oxidative addition of MeI to some cyclometalated organoplatinum(II) complexes: Kinetics and mechanism

Cited by 44 publications

References 65 publications

Secondary kinetic deuterium isotope effect in oxidative addition reaction of cycloplatinated(II) complexes with MeI

Secondary kinetic deuterium isotope effect in oxidative addition reaction of cycloplatinated(II) complexes with MeI

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands

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