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Low‐Barrier Hydrogen Bonds in Negative Thermal Expansion Material H 3 [Co(CN) 6 ]
- Source :
- Tolborg, K, Jørgensen, M R V, Sist, M, Mamakhel, M A H, Overgaard, J & Iversen, B B 2019, ' Low-Barrier Hydrogen Bonds in Negative Thermal Expansion Material H 3 [Co(CN) 6 ] ', Chemistry: A European Journal, vol. 25, no. 27, pp. 6814-6822 . https://doi.org/10.1002/chem.201900358
- Publication Year :
- 2019
- Publisher :
- Wiley, 2019.
-
Abstract
- The covalent nature of the low-barrier N−H−N hydrogen bonds in the negative thermal expansion material H 3[Co(CN) 6] has been established by using a combination of X-ray and neutron diffraction electron density analysis and theoretical calculations. This finding explains why negative thermal expansion can occur in a material not commonly considered to be built from rigid linkers. The pertinent hydrogen atom is located symmetrically between two nitrogen atoms in a double-well potential with hydrogen above the barrier for proton transfer, thus forming a low-barrier hydrogen bond. Hydrogen is covalently bonded to the two nitrogen atoms, which is the first experimentally confirmed covalent hydrogen bond in a network structure. Source function calculations established that the present N−H−N hydrogen bond follows the trends observed for negatively charge-assisted hydrogen bonds and low-barrier hydrogen bonds previously established for O−H−O hydrogen bonds. The bonding between the cobalt and cyanide ligands was found to be a typical donor–acceptor bond involving a high-field ligand and a transition metal in a low-spin configuration.
- Subjects :
- OUTLIER
Hydrogen
chemistry.chemical_element
010402 general chemistry
01 natural sciences
Catalysis
ATOMS
neutron diffraction
X-RAY-DIFFRACTION
Negative thermal expansion
WAVE-FUNCTIONS
SCATTERING
Physics::Atomic Physics
electron density
Quantitative Biology::Biomolecules
010405 organic chemistry
Hydrogen bond
Ligand
Chemistry
chemical bonding
Organic Chemistry
CHARGE-DENSITY
General Chemistry
Hydrogen atom
X-ray diffraction
0104 chemical sciences
Crystallography
Chemical bond
MODEL-COMPOUND
Covalent bond
hydrogen bonds
X-ray crystallography
NEUTRON
CATALYTIC TRIAD
Subjects
Details
- ISSN :
- 15213765 and 09476539
- Volume :
- 25
- Database :
- OpenAIRE
- Journal :
- Chemistry – A European Journal
- Accession number :
- edsair.doi.dedup.....6756101fc9ece20ce948c562e77f6c49