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Gas phase complexes MX 3·4,4′Bpy·M′X 3 (M,M′ = Al, Ga; X = Cl, Br) : Experiment and theory. / Berezovskaya, Ekaterina A.; Timoshkin, Alexey Y.; Sevastianova, Tatiana N.; Misharev, Alexander D.; Suvorov, Andrew V.; Schaefer, Henry F.
в: Journal of Physical Chemistry B, Том 108, № 28, 15.07.2004, стр. 9561-9563.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Gas phase complexes MX 3·4,4′Bpy·M′X 3 (M,M′ = Al, Ga; X = Cl, Br)
T2 - Experiment and theory
AU - Berezovskaya, Ekaterina A.
AU - Timoshkin, Alexey Y.
AU - Sevastianova, Tatiana N.
AU - Misharev, Alexander D.
AU - Suvorov, Andrew V.
AU - Schaefer, Henry F.
PY - 2004/7/15
Y1 - 2004/7/15
N2 - Donor-acceptor (DA) complexes MX 3·LL·M′X 3 (M, M′ = Al, Ga; X = Cl, Br; LL = 4,4′-bipyridyl) have been theoretically investigated at the B3LYP/pVDZ level of theory. Addition of the first molecule of MX 3 to 4,4′-bipyridyl has a similar exothermicity compared to complexes with the monodentate donor pyridine. Addition of the second molecule of MX 3 is significantly (by about 15 kJ mol -1) less exothermic. Nevertheless all 2:1 complexes (including heteroacceptor) are predicted to be stable in the vapor phase up to 660, 760, 830 and 920 K for GaBr 3, GaCl 3, AlBr 3, and AlCl 3, respectively. Four homoacceptor MX 3·4,4′bpy·MX 3 complexes have been synthesized for the first time, and their existence in the vapor phase has been proven by mass spectrometry. The theoretically predicted order of the complex stability AlCl 3 > AlBr 3 > GaCl 3 > GaBr 3 correlates well with the experimental observations of M 2X 5bpy + ion abundances in the mass spectra. The results obtained show for the first time that the synthesis of the gas-phase stable heteroacceptor complexes is feasible, which opens the prospect for their future use as single-source precursors to the stoichiometry-controlled synthesis of 13-15 alloys.
AB - Donor-acceptor (DA) complexes MX 3·LL·M′X 3 (M, M′ = Al, Ga; X = Cl, Br; LL = 4,4′-bipyridyl) have been theoretically investigated at the B3LYP/pVDZ level of theory. Addition of the first molecule of MX 3 to 4,4′-bipyridyl has a similar exothermicity compared to complexes with the monodentate donor pyridine. Addition of the second molecule of MX 3 is significantly (by about 15 kJ mol -1) less exothermic. Nevertheless all 2:1 complexes (including heteroacceptor) are predicted to be stable in the vapor phase up to 660, 760, 830 and 920 K for GaBr 3, GaCl 3, AlBr 3, and AlCl 3, respectively. Four homoacceptor MX 3·4,4′bpy·MX 3 complexes have been synthesized for the first time, and their existence in the vapor phase has been proven by mass spectrometry. The theoretically predicted order of the complex stability AlCl 3 > AlBr 3 > GaCl 3 > GaBr 3 correlates well with the experimental observations of M 2X 5bpy + ion abundances in the mass spectra. The results obtained show for the first time that the synthesis of the gas-phase stable heteroacceptor complexes is feasible, which opens the prospect for their future use as single-source precursors to the stoichiometry-controlled synthesis of 13-15 alloys.
UR - http://www.scopus.com/inward/record.url?scp=3442892369&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:3442892369
VL - 108
SP - 9561
EP - 9563
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 28
ER -
ID: 17373071