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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 and Abu-Omar, Mahdi M. 2017. Mechanism of Me–Re bond addition to Platinum(II) and dioxygen activation by the resulting Pt–Re bimetallic center. Inorganic Chemistry 56 (4) , pp. 2145-2152. 10.1021/acs.inorgchem.6b02801

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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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: American Chemical Society
ISSN: 0020-1669
Last Modified: 16 Mar 2021 16:45
URI: http://orca.cardiff.ac.uk/id/eprint/139190

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