We are exploring the effects of bulk, condensed-phase media on the structural properties of haloacetonitrile-boron trichloride complexes (XCH2CN�BCl3, X=F, Cl), using both computations and low-temperature IR spectroscopy. Both DFT and post Hartree-Fock computations indicate that two minima occur along the B-N bond coordinate, and that these minima are separated by a significant barrier. The inner (global) minima lie at B-N distances of about 1.6 � and the binding energies range from 8.7 to 1.9 kcal/mol. The outer, secondary minima are much shallower, 4.5 � 0.5 kcal/mol, and occur near B-N distances of 2.8 � to 3.1 �. We have also calculated vibrational frequencies, and these indicate that key, structurally-sensitive vibrational modes shift markedly between these two minimum energy structures. As such, we are currently obtaining low-temperature IR spectra of these complexes, both in BCl3/XCH2CN films and inert, noble gas matrices, to determine which structure exists under such conditions.

Structural properties of haloacetonitrile–BCl<sub>3</sub> complexes via computations and low-temperature IR spectroscopy

245th National Meeting (2013)

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Structural properties of haloacetonitrile–BCl3 complexes via computations and low-temperature IR spectroscopy

Structural properties of haloacetonitrile–BCl₃ complexes via computations and low-temperature IR spectroscopy