Structural and energetic properties of OC–BX3 complexes: unrealized potential for bond-stretch isomerism

Abstract

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.