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Title: A Combined Gas-Phase Photoelectron Spectroscopic and Theoretical Study of Zeise's Anion and Its Bromine and Iodine Analogues

Abstract

We report the first photoelectron spectroscopic study of Zeise’s anion, [PtCl3(C2H4)], and its Br- and I- analogs in the gas phase. Well-resolved and rich spectral features are obtained for each species, yielding detailed electronic structure information, which is assigned with the aid of highlevel electronic structure calculations at the Coupled Cluster (CC) level of theory. The electron binding energies of [PtX3(C2H4)] are found to decrease with the size of halogen (4.57, 4.51, and 4.18 eV for X = Cl, Br, and I, respectively). The calculations indicate a synergistic η2 interaction [with interaction strengths of 1.54 (Cl), 1.37 (Br) and 1.10 eV (I)] between the perpendicular C2H4 fragment and the nearly horizontal planar PtX3- anions, resulting in activating the ethylene molecule. The detailed insights of the chemical bonding and underlying electronic structure can be used to benchmark interactions between olefins and transition metal complexes, which are crucial to a wide range of catalytic processes.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1044481
Report Number(s):
PNNL-SA-86382
Journal ID: ISSN 1433-7851; 44678; KC0301020; KC0301020; TRN: US201214%%456
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition, 51(26):6356-6360
Additional Journal Information:
Journal Volume: 51; Journal Issue: 26; Journal ID: ISSN 1433-7851
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKENES; ANIONS; BENCHMARKS; BONDING; BROMINE; ELECTRONIC STRUCTURE; ELECTRONS; ETHYLENE; HALOGENS; IODINE; TRANSITION ELEMENTS; Environmental Molecular Sciences Laboratory

Citation Formats

Hou, Gaolei, Wen, Hui, Lopata, Kenneth A., Zheng, Weijun, Kowalski, Karol, Govind, Niranjan, Wang, Xue B., and Xantheas, Sotiris S. A Combined Gas-Phase Photoelectron Spectroscopic and Theoretical Study of Zeise's Anion and Its Bromine and Iodine Analogues. United States: N. p., 2012. Web. doi:10.1002/anie.201201959.
Hou, Gaolei, Wen, Hui, Lopata, Kenneth A., Zheng, Weijun, Kowalski, Karol, Govind, Niranjan, Wang, Xue B., & Xantheas, Sotiris S. A Combined Gas-Phase Photoelectron Spectroscopic and Theoretical Study of Zeise's Anion and Its Bromine and Iodine Analogues. United States. doi:10.1002/anie.201201959.
Hou, Gaolei, Wen, Hui, Lopata, Kenneth A., Zheng, Weijun, Kowalski, Karol, Govind, Niranjan, Wang, Xue B., and Xantheas, Sotiris S. Mon . "A Combined Gas-Phase Photoelectron Spectroscopic and Theoretical Study of Zeise's Anion and Its Bromine and Iodine Analogues". United States. doi:10.1002/anie.201201959.
@article{osti_1044481,
title = {A Combined Gas-Phase Photoelectron Spectroscopic and Theoretical Study of Zeise's Anion and Its Bromine and Iodine Analogues},
author = {Hou, Gaolei and Wen, Hui and Lopata, Kenneth A. and Zheng, Weijun and Kowalski, Karol and Govind, Niranjan and Wang, Xue B. and Xantheas, Sotiris S.},
abstractNote = {We report the first photoelectron spectroscopic study of Zeise’s anion, [PtCl3(C2H4)], and its Br- and I- analogs in the gas phase. Well-resolved and rich spectral features are obtained for each species, yielding detailed electronic structure information, which is assigned with the aid of highlevel electronic structure calculations at the Coupled Cluster (CC) level of theory. The electron binding energies of [PtX3(C2H4)] are found to decrease with the size of halogen (4.57, 4.51, and 4.18 eV for X = Cl, Br, and I, respectively). The calculations indicate a synergistic η2 interaction [with interaction strengths of 1.54 (Cl), 1.37 (Br) and 1.10 eV (I)] between the perpendicular C2H4 fragment and the nearly horizontal planar PtX3- anions, resulting in activating the ethylene molecule. The detailed insights of the chemical bonding and underlying electronic structure can be used to benchmark interactions between olefins and transition metal complexes, which are crucial to a wide range of catalytic processes.},
doi = {10.1002/anie.201201959},
journal = {Angewandte Chemie International Edition, 51(26):6356-6360},
issn = {1433-7851},
number = 26,
volume = 51,
place = {United States},
year = {2012},
month = {6}
}