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

We have explored the structural and energetic properties of OC-BX 3 (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-BF 3 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-BCl 3 and OC-BBr 3 , computations predict two stable minima on their B-C potential curves. The BCl 3 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-BBr 3 , 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-BCl 3 and OC-BBr 3 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-BCl 3 and OC-BBr 3 were observed. We have explored the structural and energetic properties of OC-BX 3 (X = F, Cl, or Br) complexes using computations and low-temperature infrared spectroscopy. For the OC-BCl 3 and OC-BBr 3 systems, we predict the existence of two distinct, stable structures along the B-C bond coordinate.