Proton affinities of amino group functionalizing 2D and 3D boron compounds

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F18%3A00500424" target="_blank" >RIV/61388980:_____/18:00500424 - isvavai.cz</a>

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

Proton affinities of amino group functionalizing 2D and 3D boron compounds

Original language description

We report quantum-chemical computations of Proton Affinities (PA) of icosahedral amino boranes, carboranes and Co-containing metallacarboranes with a relative error of similar to 2% when experimental data available by means of the B3LYP and BP86 functionals. Use of larger basis sets for simple systems such as NH3, CH3NH2, and borazine (B3H6N3) reduces the error to similar to 0.5 % indicating the validity of these functionals for these computations and prediction of PA for unavailable experimental data on amino-derived (car) boranes and metalla(car)boranes. The computed PA show that, from an electronic structure point of view, when substituting an exo H atom by an NH2 group in B12H12(2-), CB11H12(-), (ortho, meta, para)-C2B10H12, and the metallacarborane [3-Co(1,2-C2B9H11)(2)]((-)) = COSAN the most similar system to be compared with is the anion NH2-BH3(-) computed PA(B3LYP/cc-pVTZ) = 1505 kJ.mol(-1) rather than methylamine CH3NH2 or borazine, the two latter with experimental PA of 900 and 803 kJ.mol(-1) respectively. The largest PA for a given isomer correspond, following this order, to: 1-NH2-B12H11(2-), (-)BH3NH2, 12-NH2-CB11H11(-), cisoid 8-NH2-COSAN, transoid 9-NH2-COSAN, 9-NH2-1,2-C2B10H11, 9-NH2-1,7-C2B10H11, and 2-NH2-1,12- C2B10H11. The rule for larger PA applies for isomers with the NH2 groups farthest aways from (non-metal) carborane C(cage) atoms. Pyramidalization energy computation shows an enhanced facility for planarization of the amino group in cisoid 8-NH2-COSAN as compared to cisoid 1-NH2-COSAN.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

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Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2018

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Afinidad

ISSN

0001-9704

e-ISSN

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Volume of the periodical

75

Issue of the periodical within the volume

584

Country of publishing house

ES - SPAIN

Number of pages

7

Pages from-to

260-266

UT code for WoS article

000455195900003

EID of the result in the Scopus database

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