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Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures.

Knapp, CE; Wann, DA; Bil, A; Schirlin, JT; Robertson, HE; McMillan, PF; ... Carmalt, CJ; + view all (2012) Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures. Inorg Chem , 51 (5) 3324 - 3331. 10.1021/ic202775x.

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The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me(2)Ga(OR)](2) have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me(2)Ga(OCH(2)CH(2)NMe(2))](2) (1) and [Me(2)Ga(OCH(2)CH(2)OMe)](2) (2) adopt dimeric structures, although only the monomeric forms [Me(2)Ga(OCH(2)CH(2)NMe(2))] (1a) and [Me(2)Ga(OCH(2)CH(2)OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me(2)Ga(O(t)Bu)](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.

Title:Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures.
Location:United States
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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