[Me8Pt4ReS4]− and related PtMe2-containing clusters derived from tetrathiorhenate

Yao, Haijun; Rauchfuss, Thomas B.; Wilson, Scott R.

doi:10.1016/j.jorganchem.2004.09.010

Cited by 1 publication

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“…The Pt−Re bond is 2.8954(4) Å, which is longer than the average Pt−Re single bond indicating dative bonding. 24,25 The geometry of rhenium in 2 is trigonal bipyramidal with the three oxo ligands in one plane and the Me and Pt occupying the apical positions. The geometry around the Pt is slightly distorted square pyramid with the Pt−Re bond tilted by 7.53°from the normal to the mean square plane around platinum.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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

et al. 2017

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Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe(bpy)], (bpy = 2,2'-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid-base adduct [(bpy)MePt-Re(Me)(O)] (2) and subsequently affords the oxidative addition product [(bpy)MePtReO] (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 C 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)MePtOReO] (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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Section: ■ Results and Discussionmentioning

confidence: 99%