Structural and energetic properties of OC-BX3 complexes: unrealized potential for bond-stretch isomerism.
Phys Chem Chem Phys
; 23(27): 14678-14686, 2021 Jul 14.
Article
en En
| MEDLINE
| ID: mdl-34223854
We have explored the structural and energetic properties of OC-BX3 (X = F, Cl, or Br) complexes using computations and low-temperature infrared spectroscopy. Quantum-chemical calculations have provided equilibrium structures, binding energies, vibrational frequencies, and B-C potential energy curves. The OC-BF3 system is a weak, long-bonded complex with a single minimum on the B-C potential (R(B-C) = 2.865 Å). For the remaining two complexes, OC-BCl3 and OC-BBr3, computations predict two stable minima on their B-C potential curves. The BCl3 system is a weak complex with a long bond (R(B-C) = 3.358 Å), but it exhibits a secondary, meta-stable minimum with a short bond length of 1.659 Å. For OC-BBr3, the system is a weak complex with a relatively short bond of 1.604 Å (according to wB97X-D/aug-cc-pVTZ), but also has a secondary minimum at R(B-C) = 3.483 Å. This long-bond structure is the global minimum according to CCSD/aug-cc-pVTZ. In addition, the long-bond forms of both OC-BCl3 and OC-BBr3 were observed in matrix-isolation IR experiments. The measured CO stretching frequencies were 2145 cm-1 and 2143 cm-1, respectively. No signals due to the short-bond forms of OC-BCl3 and OC-BBr3 were observed.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Phys Chem Chem Phys
Asunto de la revista:
BIOFISICA
/
QUIMICA
Año:
2021
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Reino Unido