Matrix isolation of HGaX2 (X = Cl or Br): IR spectroscopy and ab initio calculations
Abstract
High-vacuum thermolyses of the intramolecularly co-ordinated gallanes Me2N(CH2)3GaX2 with X = Cl 1 or Br 2 were investigated with matrix isolation techniques. Among the products, which have been identified with IR spectroscopy, ab initio calculations, and known literature data, are monomeric HGaCl2 and HGaBr2. The experimental vibrational frequencies of these hydrides are compared with calculated harmonic frequencies at the MP2(fc)/6-311+G(2d,p) and B3LYP/6-311+G(2d,p) level of theory. Beside monomeric HGaX2, the argon matrices of the thermolyses experiments contained CH4, HCN, H2CCH2, H2C
NMe, [H2CCHCH2]˙, H2C
CHCH3, HX, and GaX (X = Cl or Br). In the case of GaBr the difference between the known gas-phase value and the measured IR frequency in argon matrices is discussed and explained with the help of SCRF-B3LYP calculations.