Understanding the Nature and Properties of Hydrogen-Hydrogen Bonds: The Stability of a Bulky Phosphatetrahedrane as a Case Study.
J Phys Chem A
; 125(28): 6151-6157, 2021 Jul 22.
Article
em En
| MEDLINE
| ID: mdl-34236879
ABSTRACT
Recently, the first mixed C/P phosphatetrahedranes (tBuC)3P and (tBuCP)2 were reported. Unlike (tBuCP)2, (tBuC)3P exhibits remarkable thermal stability, which can be partially attributed to a network of nine hydrogen-hydrogen bonds (HHBs) localized between the tert-butyl substituents. The stabilizing contribution arising from this network of HHBs was obtained from local energy decomposition (LED) analysis calculated at the domain-based local pair natural orbital CCSD(T) (DLPNO-CCSD(T)) level of theory. These calculations suggest that each HHB contributes approximately -0.7 kcal/mol of stabilization; however, the net stabilization energy likely lies between -0.25 and -0.5 kcal/mol because of steric repulsion. Spatial analysis of the London dispersion energy via a dispersion interaction density (DID) plot reveals that the DID surface is localized at key C-H groups involved in HHBs, consistent with London dispersion interactions predominantly arising from HHBs. In addition, we present a computed mechanism that supports a phosphinidenoid species as a key reaction intermediate in the synthesis of (tBuC)3P.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
Estados Unidos