Monochlorogallane: physical properties and structure of the gaseous molecule H2Ga(mu-Cl)2GaH2 as determined by vibrational, electron diffraction, and ab initio studies.

Abstract

Monochlorogallane, synthesized by the metathesis of gallium(III) chloride with an excess of trimethylsilane at ca. 250 K, has been characterized by chemical analysis, by its IR, Raman, and 1H NMR spectra, and by the products of its reaction with trimethylamine. The vibrational spectra of the vapor species isolated in solid Ar, N2, or CH4 matrixes at ca. 12 K imply the presence of only one species, viz. the dimer with an equilibrium structure conforming to D2h symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements augmented by the results of ab initio molecular orbital calculations. An equilibrium structure with D2h symmetry has been assumed in the analysis of the electron diffraction pattern. However, as the molecule has a very low frequency Ga(mu-Cl)2Ga ring-puckering mode, a dynamic model was used to describe it with the aid of a set of pseudoconformers spaced at even intervals (deltadelta = 5 degrees, deltamax, = 20 delta) around the ring-puckering angle delta and Boltzmann-weighted according to a quartic potential V(delta) = V4delta4 + V2delta2. The differences in bond distances and angles between the different pseudoconformers were constrained to the values derived from the ab initio calculations employing second-order Moller-Plesset (MP2) methods (with all the electrons included in the correlation calculations) and a 6-311G(d) basis set. The results for the weighted average of the principal distances (ralpha) and angles (<alpha) (with estimated 1sigma uncertainties) from the combined GED/ab initio study are r(Ga-Cl) 2.350(2) A, r(Ga-H) 1.523(20) A, <Cl-Ga-Cl 89.7(5)degrees, <H-Ga-H 135.1 degrees, V4 3.0 x 10(-6) kcal mol(-1) deg(-4), and V2 6.0 x 10(-4) kcal mol(-1) deg(-2).