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Title: Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study

Abstract

Molecular species with electron affinities (EAs) larger than that of the chlorine atom (3.6131 eV) are superhalogens. The corresponding negative ions, namely, superhalogen anions, are intrinsically very stable with high electron binding energies (EBEs), and widely exist as building blocks of bulk materials and ionic liquids. The most common superhalogen anions proposed and confirmed to date are either ionic salts or compact inorganic species. Herein we report a new class of superhalogen species, a series of tetracoordinated organoboron anions [BL4]– (L = phenyl (1), 4-fluorophenyl (2), 1-imidazolyl (3), L4 = H(pyrazolyl)3 (4)) with bulky organic ligands covalently bound to the central B atom. Negative ion photoelectron spectroscopy (NIPES) reveals all of these anions possessing EBEs higher than that of Cl- with the adiabatic / vertical detachment energy (ADE / VDE) of 4.44/4.8 (1), 4.78/5.2 (2), 5.08/5.4 (3), and 4.59/4.9 eV (4), respectively. First-principles calculations confirmed high EBEs of [BL4]– and predicted that these anions are thermodynamically stable against fragmentation. The unraveled superhalogen nature of these species provides a molecular basis to explain the wide-range applications of tetraphenylborate (TPB) (1) and trispyrazolylborate (Tp) (4) in many areas spanning from industrial waste treatment to soft material synthesis and organometallic chemistry

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1166877
Report Number(s):
PNNL-SA-98790
48036; KC0301020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A, 118(37):8074-8080
Additional Journal Information:
Journal Name: Journal of Physical Chemistry A, 118(37):8074-8080
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Zhang, Jian, Yang, Ping, Sun, Zhenrong, and Wang, Xue B. Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study. United States: N. p., 2014. Web. doi:10.1021/jp410009a.
Zhang, Jian, Yang, Ping, Sun, Zhenrong, & Wang, Xue B. Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study. United States. https://doi.org/10.1021/jp410009a
Zhang, Jian, Yang, Ping, Sun, Zhenrong, and Wang, Xue B. 2014. "Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study". United States. https://doi.org/10.1021/jp410009a.
@article{osti_1166877,
title = {Covalently Bound Tetracoordinated Organoborons are Superhalogens: A Combined Negative Ion Photoelectron Spectroscopy and Theoretical Study},
author = {Zhang, Jian and Yang, Ping and Sun, Zhenrong and Wang, Xue B.},
abstractNote = {Molecular species with electron affinities (EAs) larger than that of the chlorine atom (3.6131 eV) are superhalogens. The corresponding negative ions, namely, superhalogen anions, are intrinsically very stable with high electron binding energies (EBEs), and widely exist as building blocks of bulk materials and ionic liquids. The most common superhalogen anions proposed and confirmed to date are either ionic salts or compact inorganic species. Herein we report a new class of superhalogen species, a series of tetracoordinated organoboron anions [BL4]– (L = phenyl (1), 4-fluorophenyl (2), 1-imidazolyl (3), L4 = H(pyrazolyl)3 (4)) with bulky organic ligands covalently bound to the central B atom. Negative ion photoelectron spectroscopy (NIPES) reveals all of these anions possessing EBEs higher than that of Cl- with the adiabatic / vertical detachment energy (ADE / VDE) of 4.44/4.8 (1), 4.78/5.2 (2), 5.08/5.4 (3), and 4.59/4.9 eV (4), respectively. First-principles calculations confirmed high EBEs of [BL4]– and predicted that these anions are thermodynamically stable against fragmentation. The unraveled superhalogen nature of these species provides a molecular basis to explain the wide-range applications of tetraphenylborate (TPB) (1) and trispyrazolylborate (Tp) (4) in many areas spanning from industrial waste treatment to soft material synthesis and organometallic chemistry},
doi = {10.1021/jp410009a},
url = {https://www.osti.gov/biblio/1166877}, journal = {Journal of Physical Chemistry A, 118(37):8074-8080},
number = ,
volume = ,
place = {United States},
year = {Thu Sep 18 00:00:00 EDT 2014},
month = {Thu Sep 18 00:00:00 EDT 2014}
}