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:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- 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:
- Journal Article: 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.
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
Haiges, Ralf, Deokar, Piyush, Vasiliu, Monica, Stein, Trent H., Dixon, David A., and Christe, Karl O. 2017.
"Preparation and Characterization of Group 13 Cyanides". United States. https://doi.org/10.1002/chem.201700611. https://www.osti.gov/servlets/purl/1388369.
@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},
url = {https://www.osti.gov/biblio/1388369},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
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}
}
Web of Science
Works referenced in this record:
2D NMR exchange spectroscopy with spy nuclei for thallium(III) cyano complexes in aqueous solution
journal, July 1993
- Batta, Gyula; Banyai, Istvan; Glaser, Julius
- Journal of the American Chemical Society, Vol. 115, Issue 15
Magnetic Interactions and Magnetic Anisotropy in Exchange Coupled 4f-3d Systems: A Case Study of a Heterodinuclear Ce 3+ -Fe 3+ Cyanide-Bridged Complex
journal, January 2009
- Sorace, Lorenzo; Sangregorio, Claudio; Figuerola, Albert
- Chemistry - A European Journal, Vol. 15, Issue 6
Structure of tribromotris(pyridine)thallium(III), [TlBr3(C5H5N)3]
journal, November 1984
- Jeffs, S. E.; Small, R. W. H.; Worrall, I. J.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 11
Directed Assembly of Metal−Cyanide Cluster Magnets
journal, April 2005
- Beltran, Lianne M. C.; Long, Jeffrey R.
- Accounts of Chemical Research, Vol. 38, Issue 4
Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3⋅CH3CN (M=Ga, In, Tl), [Ga(N3)5]2−, and [M(N3)6]3− (M=In, Tl)
journal, July 2011
- Haiges, Ralf; Boatz, Jerry A.; Williams, Jodi M.
- Angewandte Chemie, Vol. 123, Issue 38
AB initio and Dft investigations of Al, Ga, and In tricyanides and triisocyanides
journal, July 2000
- Timoshkin, A. Yu.; Schaefer, H. F.
- Journal of Structural Chemistry, Vol. 41, Issue 1
Tricyanometalate molecular chemistry: A type of versatile building blocks for the construction of cyano-bridged molecular architectures
journal, August 2011
- Wang, Shi; Ding, Xue-Hua; Zuo, Jing-Lin
- Coordination Chemistry Reviews, Vol. 255, Issue 15-16
Theoretical models incorporating electron correlation
journal, January 1976
- Pople, John A.; Binkley, J. Stephen; Seeger, Rolf
- International Journal of Quantum Chemistry, Vol. 10, Issue S10
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient
journal, January 1993
- Klamt, A.; Schüürmann, G.
- J. Chem. Soc., Perkin Trans. 2, Issue 5
Crystal structure of cyanometallates Me 3 [ Co ( CN ) 6 ] 2 and KMe [ Fe ( CN ) 6 ] with Me = Mn 2+ , Ni 2+ , Cu 2+
journal, March 1999
- Małecki, Grzegorz; Ratuszna, Alicja
- Powder Diffraction, Vol. 14, Issue 1
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992
- Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
- The Journal of Chemical Physics, Vol. 96, Issue 9
Structure of Thallium(III) Chloride, Bromide, and Cyanide Complexes in Aqueous Solution
journal, May 1995
- Blixt, Johan; Glaser, Julius; Mink, Janos
- Journal of the American Chemical Society, Vol. 117, Issue 18
Schwingungsspektren der Cyanodimethylmetall-Komplexe von Magnesium, Aluminium, Gallium und Indium
journal, February 1975
- Müller, Joachim; Schmock, Fritjof; Klopsch, Achim
- Chemische Berichte, Vol. 108, Issue 2
Preparation and structures of two mixed-ligand 4-methylpyridine indium bromide complexes
journal, February 2016
- Masnovi, John; Clark, Eric B.; Hepp, Aloysius F.
- Journal of Molecular Structure, Vol. 1105
Solubility, Complex Formation, and Redox Reactions in the Tl 2 O 3 −HCN/CN - −H 2 O System. Crystal Structures of the Cyano Compounds Tl(CN) 3 ·H 2 O, Na[Tl(CN) 4 ]·3H 2 O, K[Tl(CN) 4 ], and Tl I [Tl III (CN) 4 ] and of Tl I 2 C 2 O 4 †
journal, April 2005
- Nagy, Péter; Fischer, Andreas; Glaser, Julius
- Inorganic Chemistry, Vol. 44, Issue 7
Molecules to build solids: high TC molecule-based magnets by design and recent revival of cyano complexes chemistry
journal, September 1999
- Verdaguer, Michel; Bleuzen, A.; Marvaud, V.
- Coordination Chemistry Reviews, Vol. 190-192
Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSe x
journal, August 2015
- Holligan, Kareem; Rogler, Patrick; Rehe, David
- Inorganic Chemistry, Vol. 54, Issue 18
Magnetism of metal cyanide networks assembled at interfaces
journal, December 2005
- Culp, Jeffrey T.; Park, Ju-Hyun; Frye, Franz
- Coordination Chemistry Reviews, Vol. 249, Issue 23
Metal-organic frameworks
journal, January 2003
- James, Stuart L.
- Chemical Society Reviews, Vol. 32, Issue 5
Structure of tribromobis(pyridine)thallium(III), TlBr3(C5H5N)2
journal, January 1984
- Jeffs, S. E.; Small, R. W. H.; Worrall, I. J.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 1
Molecular core-valence correlation effects involving the post-d elements Ga–Rn: Benchmarks and new pseudopotential-based correlation consistent basis sets
journal, November 2010
- Peterson, Kirk A.; Yousaf, Kazim E.
- The Journal of Chemical Physics, Vol. 133, Issue 17
Cyanometallates as Halogen Bond Acceptors
journal, December 2011
- Ormond-Prout, Johnathan E.; Smart, Paul; Brammer, Lee
- Crystal Growth & Design, Vol. 12, Issue 1
Inorganic−Organic Hybrid Molecular Architectures of Cyanometalate Host and Organic Guest Systems: Specific Behavior of the Guests
journal, April 2005
- Nishikiori, Shin-ichi; Yoshikawa, Hirofumi; Sano, Yuriko
- Accounts of Chemical Research, Vol. 38, Issue 4
Synthetic Routes to Ga(CN) 3 and MGa(CN) 4 (M = Li, Cu) Framework Structures
journal, July 1997
- Brousseau, Louis C.; Williams, Darrick; Kouvetakis, J.
- Journal of the American Chemical Society, Vol. 119, Issue 27
Formation and structure of novel ternary complexes of thallium(III)-cyanide–amine (ethylenediamine and triethylenetetramine) in solution and in solid
journal, February 2003
- Ma, Guibin; Fischer, Andreas; Ilyukhin, Andrey
- Inorganica Chimica Acta, Vol. 344
Designer Magnets Containing Cyanides and Nitriles
journal, July 2001
- Miller, Joel S.; Manson, Jamie L.
- Accounts of Chemical Research, Vol. 34, Issue 7
Cyano-Bridged Re 6 Q 8 (Q = S, Se) Cluster-Metal Framework Solids: A New Class of Porous Materials
journal, December 1998
- Beauvais, Laurance G.; Shores, Matthew P.; Long, Jeffrey R.
- Chemistry of Materials, Vol. 10, Issue 12
Quantum Mechanical Continuum Solvation Models
journal, August 2005
- Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
- Chemical Reviews, Vol. 105, Issue 8
Organoindium azides: new precursors to indium nitride
journal, December 1997
- Fischer, Roland A.; Sussek, Harald; Miehr, Alexander
- Journal of Organometallic Chemistry, Vol. 548, Issue 1
Synthesis and magnetism of multi-dimensional cyanide-bridged bimetallic assemblies
journal, March 2000
- Ohba, Masaaki; Ōkawa, Hisashi
- Coordination Chemistry Reviews, Vol. 198, Issue 1
Studies on two interesting microporous polymeric clusters {[Et4N]2[MS4Cu4(CN)4]}n (M = Mo or W) with three-dimensional open frameworks: synthesis, structural characterization, strong optical non-linearities and large optical limiting properties
journal, January 2000
- Zhang, Chi; Song, Yinglin; Xu, Yan
- Journal of the Chemical Society, Dalton Transactions, Issue 16
Indium tricyanide and indium trithiocyanate
journal, January 1966
- Goggin, P. L.; McColm, I. J.; Shore, R.
- Journal of the Chemical Society A: Inorganic, Physical, Theoretical
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Equilibrium Dynamics in the Thallium(III)−Cyanide System in Aqueous Solution
journal, December 1997
- Bányai, István; Glaser, Julius; Losonczi, Judit
- Inorganic Chemistry, Vol. 36, Issue 25
Systematically convergent basis sets with relativistic pseudopotentials. I. Correlation consistent basis sets for the post- d group 13–15 elements
journal, December 2003
- Peterson, Kirk A.
- The Journal of Chemical Physics, Vol. 119, Issue 21
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
The Disordered Crystal Structures of Zn(CN)2and Ga(CN)3
journal, November 1997
- Williams, D. J.; Partin, D. E.; Lincoln, F. J.
- Journal of Solid State Chemistry, Vol. 134, Issue 1
Die Kristallstruktur von [(CH3)2InCN]∞
journal, February 1993
- Blank, J.; Hausen, H. -D.; Weidlein, J.
- Journal of Organometallic Chemistry, Vol. 444, Issue 1-2
Synthesis of Nanoporous Cubic In(CN) 3 and In 1 - x Ga x (CN) 3 and Corresponding Inclusion Compounds
journal, September 1998
- Williams, Darrick; Kouvetakis, J.; O'Keeffe, M.
- Inorganic Chemistry, Vol. 37, Issue 18
Design of single chain magnets through cyanide-bearing six-coordinate complexes
journal, December 2005
- Lescouëzec, Rodrigue; Toma, Luminita Marilena; Vaissermann, Jacqueline
- Coordination Chemistry Reviews, Vol. 249, Issue 23
Synthesis of Molecular Adducts of Beryllium, Boron, and Gallium Cyanides: Theoretical and Experimental Correlations between Solid-State and Molecular Analogues
journal, November 2007
- Chizmeshya, A. V. G.; Ritter, C. J.; Groy, T. L.
- Chemistry of Materials, Vol. 19, Issue 24
Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3⋅CH3CN (M=Ga, In, Tl), [Ga(N3)5]2−, and [M(N3)6]3− (M=In, Tl)
journal, July 2011
- Haiges, Ralf; Boatz, Jerry A.; Williams, Jodi M.
- Angewandte Chemie International Edition, Vol. 50, Issue 38
Structures and Stability of Molecular InBr 3 Py x ( x = 1–3) Complexes: Unexpected Solid State Stabilization of Dimeric In 2 Br 6 Py 4 As Compared to Valence-Isoelectronic Group 15 and 17 Halogen Bridging Dimers
journal, November 2013
- Kazakov, Igor V.; Bodensteiner, Michael; Lisovenko, Anna S.
- Inorganic Chemistry, Vol. 52, Issue 22
Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited
journal, December 2002
- Peterson, Kirk A.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 117, Issue 23
Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2′-Bipyridine Adducts
journal, August 2016
- Deokar, Piyush; Leitz, Dominik; Stein, Trent H.
- Chemistry - A European Journal, Vol. 22, Issue 37
Cyanide Exchange on Tl(CN)4− in Aqueous Solution Studied by205Tl and13C NMR Spectroscopy
journal, July 2001
- Bányai, István; Glaser, Julius; Tóth, Imre
- European Journal of Inorganic Chemistry, Vol. 2001, Issue 7
The Hexacyanotitanate Ion: Synthesis and Crystal Structure of [NEt 4 ] 3 [Ti III (CN) 6 ]·4MeCN
journal, July 1997
- Entley, William R.; Treadway, Christopher R.; Wilson, Scott R.
- Journal of the American Chemical Society, Vol. 119, Issue 27
Emission, Raman Spectroscopy, and Structural Characterization of Actinide Tetracyanometallates
journal, April 2013
- Maynard, Branson A.; Lynn, K. Sabrina; Sykora, Richard E.
- Inorganic Chemistry, Vol. 52, Issue 9
A Decade of Octacyanides in Polynuclear Molecular Materials
journal, December 2010
- Sieklucka, Barbara; Podgajny, Robert; Korzeniak, Tomasz
- European Journal of Inorganic Chemistry, Vol. 2011, Issue 3
Synthesis and characterization of halogeno- and pseudo-halogeno-thallium(III) porphyrin complexes. Variation of the co-ordination geometry as a function of the axial ligand
journal, January 1993
- Senge, Mathias O.; Ruhlandt-Senge, Karin; Regli, Kevin J.
- Journal of the Chemical Society, Dalton Transactions, Issue 23
Thallium(III) coordination compounds: chemical information from 205 Tl NMR longitudinal relaxation times
journal, September 2002
- Bodor, Andrea; Bányai, István; Kowalewski, Jozef
- Magnetic Resonance in Chemistry, Vol. 40, Issue 11
Structure of the 4:1 complexes formed by pyridine and the Group III halides InCl3 and TlCl3: mer-trichlorotris(pyridine)indium(III)–pyridine (1/1), [InCl3(C5H5N)3].C5H5N, and mer-trichlorotris(pyridine)thallium(III)–pyridine (1/1), [TlCl3(C5H5N)3].C5H5N
journal, August 1984
- Jeffs, S. E.; Small, R. W. H.; Worrall, I. J.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 40, Issue 8
Cyanide complexes of the early transition metals (groups IVa-VIIa)
journal, November 1975
- Griffith, W. P.
- Coordination Chemistry Reviews, Vol. 17, Issue 2-3, p. 177-247
Chemistry and magnetism of cyanido-bridged d–f assemblies
journal, October 2006
- Tanase, Stefania; Reedijk, Jan
- Coordination Chemistry Reviews, Vol. 250, Issue 19-20
Molecular spin crossover phenomenon: recent achievements and prospects
journal, January 2011
- Bousseksou, Azzedine; Molnár, Gábor; Salmon, Lionel
- Chemical Society Reviews, Vol. 40, Issue 6
Cyanide-Bridged Molecular Squares - The Building Units of Prussian Blue
journal, June 2011
- Newton, Graham N.; Nihei, Masayuki; Oshio, Hiroki
- European Journal of Inorganic Chemistry, Vol. 2011, Issue 20
Tailored Design of Multiple Nanoarchitectures in Metal-Cyanide Hybrid Coordination Polymers
journal, December 2012
- Hu, Ming; Belik, Alexei A.; Imura, Masataka
- Journal of the American Chemical Society, Vol. 135, Issue 1
Molecular structure of an indium(III) iodide-tris(4-methylpyridine) adduct
journal, June 1996
- Brown, Martyn A.; Tuck, Dennis G.
- Inorganica Chimica Acta, Vol. 247, Issue 1
Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934
- Møller, Chr.; Plesset, M. S.
- Physical Review, Vol. 46, Issue 7
Photomagnetism in Cyano-Bridged Bimetal Assemblies
journal, August 2012
- Ohkoshi, Shin-ichi; Tokoro, Hiroko
- Accounts of Chemical Research, Vol. 45, Issue 10
Organo-Tricyanoborates as Tectons: Illustrative Coordination Polymers Based on Copper(I) Derivatives
journal, September 2005
- Yao, Haijun; Kuhlman, Matthew L.; Rauchfuss, Thomas B.
- Inorganic Chemistry, Vol. 44, Issue 18
Topological Motifs in Cyanometallates: From Building Units to Three-Periodic Frameworks
journal, October 2015
- Alexandrov, Eugeny V.; Virovets, Alexander V.; Blatov, Vladislav A.
- Chemical Reviews, Vol. 115, Issue 22
Inorganic—Organic Hybrid Molecular Architectures of Cyanometalate Host and Organic Guest Systems: Specific Behavior of the Guests
journal, July 2005
- Nishikiori, Shin-Ichi; Yoshikawa, Hirofumi; Sano, Yuriko
- ChemInform, Vol. 36, Issue 28
Directed Assembly of Metal—Cyanide Cluster Magnets
journal, July 2005
- Beltran, Lianne M. C.; Long, Jeffrey R.
- ChemInform, Vol. 36, Issue 29
Quantum Mechanical Continuum Solvation Models
journal, October 2005
- Tomasi, Jacopo; Menucci, Benedetta; Cammi, Roberto
- ChemInform, Vol. 36, Issue 42
Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays
journal, May 2020
- Smolentsev, Grigory; Milne, Christopher J.; Guda, Alexander
- Nature Communications, Vol. 11, Issue 1
Metal-Organic Frameworks
journal, September 2006
- Kaskel, Stefan
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 632, Issue 12-13
Equilibrium Dynamics in the Thallium(III)-Cyanide System in Aqueous Solution.
journal, February 1998
- Bányai, Istv́an; Glaser, Julius; Losonczi, Judit
- Inorganic Chemistry, Vol. 37, Issue 5
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988
- Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
- The University of North Carolina at Chapel Hill University Libraries
Works referencing / citing this record:
Substitution Reactions at Dipp BIAN Supported Fluoroantimony Cations Yielding Cyanoantimony and Azidoantimony Cations
journal, November 2017
- Suter, Riccardo; Frazee, Christopher; Burford, Neil
- Chemistry - A European Journal, Vol. 23, Issue 68