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Publication Detail
Dimethylalkoxygallanes: Monomeric versus dimeric gas-phase structures
Abstract
The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me Ga(OR)] have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me Ga(OCH CH NMe )] (1) and [Me Ga(OCH CH OMe)] (2) adopt dimeric structures, although only the monomeric forms [Me Ga(OCH CH NMe )] (1a) and [Me Ga(OCH CH OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me Ga(O Bu)] (3) was also studied by gas electron diffraction. In contrast to 1 and 2, compound 3 is dimeric in the gas phase, as well as in the solid state. The gas-phase structures of 1a and 2a exhibit five-membered rings formed by a dative bond between Ga and the donor atom (N or O) from the donor-functionalized alkoxide. In 3 there is no possibility of a monomeric structure being stabilized by the formation of such a dative bond since only a monofunctional alkoxide is present in the molecule. © 2012 American Chemical Society.
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