Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures

Caroline E. Knapp, Derek A. Wann, Andrzej Bil, Julien T. Schirlin, Heather E. Robertson, Paul F. Mcmillan, David W. H. Rankin, Claire J. Carmalt

Research output: Contribution to journalArticlepeer-review

Abstract

The molecular structures of the vapors produced on heating dimethyl-alkoxygallanes of the type [Me2Ga(OR)]2 have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me2Ga(OCH2CH2NMe2)]2 (1) and [Me2Ga(OCH2CH2OMe)]2 (2) adopt dimeric structures, although only the monomeric forms [Me2Ga(OCH2CH2NMe2)] (1a) and [Me2Ga(OCH2CH2OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me2Ga(OtBu)]2 (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.

Original languageEnglish
Pages (from-to)3324-3331
JournalInorganic Chemistry
Volume51
Issue number5
DOIs
Publication statusPublished - 5 Mar 2012

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