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

Abstract

Unusual cis-oxidative addition of methyltrioxorhenium (MTO) to [PtMe 2(bpy)], (bpy = 2,2'-bipyridine) (1) is described. Addition of MTO to 1 first gives the Lewis acid–base adduct [(bpy)Me 2Pt–Re(Me)(O) 3] (2) and subsequently affords the oxidative addition product [(bpy)Me 3PtReO 3] (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)Me 3PtOReO 3] (4) as final product. In conclusion, 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.'

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [1];  [1];  [1];  [4];  [5];  [3];  [3]; ORCiD logo [6]
  1. Purdue Univ., West Lafayette, IN (United States). Brown Lab., Dept. of Chemistry
  2. Hamad Bin Khalifa Univ., Doha (Qatar). Qatar Environment and Energy Research Inst.
  3. Shiraz Univ. (Iran). College of Sciences, Dept. of Chemistry
  4. Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering
  5. Purdue Univ., West Lafayette, IN (United States). Brown Lab., Dept. of Chemistry; Hamad Bin Khalifa Univ., Doha (Qatar). Qatar Environment and Energy Research Inst.
  6. Purdue Univ., West Lafayette, IN (United States). Brown Lab., Dept. of Chemistry; Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Qatar National Research Foundation (QNRF); Iran National Science Foundation; Shiraz University Research Council
OSTI Identifier:
1351373
DOE Contract Number:
AC02-06CH11357; FG02-06ER15794; NPRP 6-370-1-075; 93038832
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 56; Journal Issue: 4
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

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.. Mechanism of Me–Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt–Re Bimetallic Center. United States: N. p., 2017. Web. doi: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. United States. doi: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, and Abu-Omar, Mahdi M.. Mon . "Mechanism of Me–Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt–Re Bimetallic Center". United States. doi:10.1021/acs.inorgchem.6b02801.
@article{osti_1351373,
title = {Mechanism of Me–Re Bond Addition to Platinum(II) and Dioxygen Activation by the Resulting Pt–Re Bimetallic Center},
author = {Pichaandi, Kothanda Rama and Kabalan, Lara and Amini, Hashem and Zhang, Guanghui and Zhu, Hanyu and Kenttämaa, Hilkka I. and Fanwick, Phillip E. and Miller, Jeffrey T. and Kais, Sabre and Nabavizadeh, S. Masoud and Rashdi, Mehdi and Abu-Omar, Mahdi M.},
abstractNote = {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. In conclusion, 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.'},
doi = {10.1021/acs.inorgchem.6b02801},
journal = {Inorganic Chemistry},
number = 4,
volume = 56,
place = {United States},
year = {Mon Feb 06 00:00:00 EST 2017},
month = {Mon Feb 06 00:00:00 EST 2017}
}