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Title: Preparation and Characterization of Group 13 Cyanides

Abstract

Abstract Binary Group 13 cyanides [PPh 4 ][Ga(CN) 4 ], [PPh 4 ] 2 [In(CN) 5 ], and [PPh 4 ] 2 [Tl(CN) 5 ] were obtained in quantitative yields from the corresponding metal trifluorides MF 3 (M=Ga, In, Tl) by fluoride–cyanide exchange reactions with Me 3 SiCN in the presence of stoichiometric amounts of [PPh 4 ]CN in acetonitrile solution. The 2,2′‐bipyridine (bipy) adducts [(bipy) 2 Ga(CN) 2 ][Ga(CN) 4 ], [(bipy)In(CN) 3 ], and [(bipy)Tl(CN) 3 ] were obtained from the reaction of MF 3 with Me 3 SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me 3 SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF 3 with Me 3 SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py) 2 Ga(CN) 3 ], [(py) 3 In(CN) 3 ], and [(py) 2 Tl(CN) 3 ]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X‐ray crystal structures.

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [2]; ORCiD logo [1]
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  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. The Univ. of Alabama, Tuscaloosa, AL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388369
Alternate Identifier(s):
OSTI ID: 1401775
Grant/Contract Number:  
SC0012577
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 38; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); density functional calculations; gallium; indium; thallium

Citation Formats

Haiges, Ralf, Deokar, Piyush, Vasiliu, Monica, Stein, Trent H., Dixon, David A., and Christe, Karl O. Preparation and Characterization of Group 13 Cyanides. United States: N. p., 2017. Web. doi:10.1002/chem.201700611.
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Haiges, Ralf, Deokar, Piyush, Vasiliu, Monica, Stein, Trent H., Dixon, David A., & Christe, Karl O. Preparation and Characterization of Group 13 Cyanides. United States. https://doi.org/10.1002/chem.201700611
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Haiges, Ralf, Deokar, Piyush, Vasiliu, Monica, Stein, Trent H., Dixon, David A., and Christe, Karl O. Sun . "Preparation and Characterization of Group 13 Cyanides". United States. https://doi.org/10.1002/chem.201700611. https://www.osti.gov/servlets/purl/1388369.
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@article{osti_1388369,
title = {Preparation and Characterization of Group 13 Cyanides},
author = {Haiges, Ralf and Deokar, Piyush and Vasiliu, Monica and Stein, Trent H. and Dixon, David A. and Christe, Karl O.},
abstractNote = {Abstract Binary Group 13 cyanides [PPh 4 ][Ga(CN) 4 ], [PPh 4 ] 2 [In(CN) 5 ], and [PPh 4 ] 2 [Tl(CN) 5 ] were obtained in quantitative yields from the corresponding metal trifluorides MF 3 (M=Ga, In, Tl) by fluoride–cyanide exchange reactions with Me 3 SiCN in the presence of stoichiometric amounts of [PPh 4 ]CN in acetonitrile solution. The 2,2′‐bipyridine (bipy) adducts [(bipy) 2 Ga(CN) 2 ][Ga(CN) 4 ], [(bipy)In(CN) 3 ], and [(bipy)Tl(CN) 3 ] were obtained from the reaction of MF 3 with Me 3 SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me 3 SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF 3 with Me 3 SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py) 2 Ga(CN) 3 ], [(py) 3 In(CN) 3 ], and [(py) 2 Tl(CN) 3 ]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X‐ray crystal structures.},
doi = {10.1002/chem.201700611},
journal = {Chemistry - A European Journal},
number = 38,
volume = 23,
place = {United States},
year = {Sun Apr 02 00:00:00 EDT 2017},
month = {Sun Apr 02 00:00:00 EDT 2017}
}
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