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Title: Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl 3(C 2H 4) - with Heavier Halides (Br , I - )

Abstract

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl nX 3-n(C 2H 4) - (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl 3(C 2H 4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl 3) > 4.56 (–Cl 2Br) > 4.53 (–ClBr 2) > 4.34 (–Cl 2I) > 4.30 eV (–ClI 2). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl 2X, and the trans-isomer for –ClX 2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K8-88, Richland, Washington 99352, United States
  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, MS K8-91, Richland, Washington 99352, United States
  3. Advanced Computing, Mathematics and Data Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, Washington 99352 United States; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1427905
Report Number(s):
PNNL-SA-129320
Journal ID: ISSN 1089-5639; 48584; KC0301050; KC0301050
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 122; Journal Issue: 5
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Hou, Gao-Lei, Govind, Niranjan, Xantheas, Sotiris S., and Wang, Xue-Bin. Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br–, I- ). United States: N. p., 2018. Web. doi:10.1021/acs.jpca.7b10808.
Hou, Gao-Lei, Govind, Niranjan, Xantheas, Sotiris S., & Wang, Xue-Bin. Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br–, I- ). United States. doi:10.1021/acs.jpca.7b10808.
Hou, Gao-Lei, Govind, Niranjan, Xantheas, Sotiris S., and Wang, Xue-Bin. Tue . "Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br–, I- )". United States. doi:10.1021/acs.jpca.7b10808.
@article{osti_1427905,
title = {Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br–, I- )},
author = {Hou, Gao-Lei and Govind, Niranjan and Xantheas, Sotiris S. and Wang, Xue-Bin},
abstractNote = {Four new Zeise’s family ions with mixed-halide ligands, i.e., PtClnX3-n(C2H4)- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl3(C2H4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl3) > 4.56 (–Cl2Br) > 4.53 (–ClBr2) > 4.34 (–Cl2I) > 4.30 eV (–ClI2). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl2X, and the trans-isomer for –ClX2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.},
doi = {10.1021/acs.jpca.7b10808},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 5,
volume = 122,
place = {United States},
year = {Tue Jan 16 00:00:00 EST 2018},
month = {Tue Jan 16 00:00:00 EST 2018}
}