Mechanism of Me-Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt-Re Bimetallic Center

Kothanda Rama Pichaandi, Lara Kabalan, Hashem Amini, Guanghui Zhang, Hanyu Zhu, Hilkka I. Kenttämaa, Phillip E. Fanwick, Jeffrey T. Miller, Sabre Kais, S. Masoud Nabavizadeh, Mehdi Rashdi, Mahdi M. Abu-Omar

Research output: Contribution to journalArticle

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Abstract

Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe2(bpy)], (bpy = 2,2′-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid-base adduct [(bpy)Me2Pt-Re(Me)(O)3] (2) and subsequently affords the oxidative addition product [(bpy)Me3PtReO3] (3). All complexes 1, MTO, 2, and 3 are in equilibrium in solution. The structure of 2 was confirmed by X-ray crystallography, and its dissociation constant in solution is 0.87 M. The structure of 3 was confirmed by extended X-ray absorption fine structure and X-ray absorption near-edge structure in tandem with one- and two-dimensional NMR spectroscopy augmented by deuterium and 13C isotope-labeling studies. Kinetics of formation of compound 3 revealed saturation kinetics dependence on [MTO] and first-order in [Pt], complying with prior equilibrium formation of 2 with oxidative addition of Me-Re being the rate-determining step. Exposure of 3 to molecular oxygen or air resulted in the insertion of an oxygen atom into the platinum-rhenium bond forming [(bpy)Me3PtOReO3] (4) as final product. Density functional theory analysis on oxygen insertion pathways leading to complex 4, merited on the basis of Russell oxidation pathway, revealed the involvement of rhenium peroxo species.

Original languageEnglish
Pages (from-to)2145-2152
Number of pages8
JournalInorganic Chemistry
Volume56
Issue number4
DOIs
Publication statusPublished - 20 Feb 2017

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Platinum
platinum
Chemical activation
activation
Oxygen
Rhenium
X ray absorption
rhenium
insertion
Lewis Bases
X-Rays
Isotope Labeling
Lewis Acids
Kinetics
x rays
Molecular oxygen
Deuterium
X ray crystallography
X Ray Crystallography
kinetics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Mechanism of Me-Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt-Re Bimetallic Center. / Pichaandi, Kothanda Rama; Kabalan, Lara; Amini, Hashem; Zhang, Guanghui; Zhu, Hanyu; Kenttämaa, Hilkka I.; Fanwick, Phillip E.; Miller, Jeffrey T.; Kais, Sabre; Nabavizadeh, S. Masoud; Rashdi, Mehdi; Abu-Omar, Mahdi M.

In: Inorganic Chemistry, Vol. 56, No. 4, 20.02.2017, p. 2145-2152.

Research output: Contribution to journalArticle

Pichaandi, KR, Kabalan, L, Amini, H, Zhang, G, Zhu, H, Kenttämaa, HI, Fanwick, PE, Miller, JT, Kais, S, Nabavizadeh, SM, Rashdi, M & Abu-Omar, MM 2017, 'Mechanism of Me-Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt-Re Bimetallic Center', Inorganic Chemistry, vol. 56, no. 4, pp. 2145-2152. https://doi.org/10.1021/acs.inorgchem.6b02801
Pichaandi, Kothanda Rama ; Kabalan, Lara ; Amini, Hashem ; Zhang, Guanghui ; Zhu, Hanyu ; Kenttämaa, Hilkka I. ; Fanwick, Phillip E. ; Miller, Jeffrey T. ; Kais, Sabre ; Nabavizadeh, S. Masoud ; Rashdi, Mehdi ; Abu-Omar, Mahdi M. / Mechanism of Me-Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt-Re Bimetallic Center. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 4. pp. 2145-2152.
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abstract = "Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe2(bpy)], (bpy = 2,2′-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid-base adduct [(bpy)Me2Pt-Re(Me)(O)3] (2) and subsequently affords the oxidative addition product [(bpy)Me3PtReO3] (3). All complexes 1, MTO, 2, and 3 are in equilibrium in solution. The structure of 2 was confirmed by X-ray crystallography, and its dissociation constant in solution is 0.87 M. The structure of 3 was confirmed by extended X-ray absorption fine structure and X-ray absorption near-edge structure in tandem with one- and two-dimensional NMR spectroscopy augmented by deuterium and 13C isotope-labeling studies. Kinetics of formation of compound 3 revealed saturation kinetics dependence on [MTO] and first-order in [Pt], complying with prior equilibrium formation of 2 with oxidative addition of Me-Re being the rate-determining step. Exposure of 3 to molecular oxygen or air resulted in the insertion of an oxygen atom into the platinum-rhenium bond forming [(bpy)Me3PtOReO3] (4) as final product. Density functional theory analysis on oxygen insertion pathways leading to complex 4, merited on the basis of Russell oxidation pathway, revealed the involvement of rhenium peroxo species.",
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AU - Kabalan, Lara

AU - Amini, Hashem

AU - Zhang, Guanghui

AU - Zhu, Hanyu

AU - Kenttämaa, Hilkka I.

AU - Fanwick, Phillip E.

AU - Miller, Jeffrey T.

AU - Kais, Sabre

AU - Nabavizadeh, S. Masoud

AU - Rashdi, Mehdi

AU - Abu-Omar, Mahdi M.

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AB - Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe2(bpy)], (bpy = 2,2′-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid-base adduct [(bpy)Me2Pt-Re(Me)(O)3] (2) and subsequently affords the oxidative addition product [(bpy)Me3PtReO3] (3). All complexes 1, MTO, 2, and 3 are in equilibrium in solution. The structure of 2 was confirmed by X-ray crystallography, and its dissociation constant in solution is 0.87 M. The structure of 3 was confirmed by extended X-ray absorption fine structure and X-ray absorption near-edge structure in tandem with one- and two-dimensional NMR spectroscopy augmented by deuterium and 13C isotope-labeling studies. Kinetics of formation of compound 3 revealed saturation kinetics dependence on [MTO] and first-order in [Pt], complying with prior equilibrium formation of 2 with oxidative addition of Me-Re being the rate-determining step. Exposure of 3 to molecular oxygen or air resulted in the insertion of an oxygen atom into the platinum-rhenium bond forming [(bpy)Me3PtOReO3] (4) as final product. Density functional theory analysis on oxygen insertion pathways leading to complex 4, merited on the basis of Russell oxidation pathway, revealed the involvement of rhenium peroxo species.

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