TY - JOUR

T1 - Aluminum-nitrogen rings and cages with organic handles

T2 - A theoretical study

AU - Trinh, Cong

AU - Timoshkin, Alexey Y.

AU - Frenking, Gemot

PY - 2009/4/9

Y1 - 2009/4/9

N2 - The structures and stability of monomelic and oligomeric compounds resulting from the elimination of 2 mol of HBr from the AlBr3en complex have been studied theoretically at the B3LYP/LANL2DZ(d,p) level of theory. Two series of the ring and cage oligomer compounds were considered: imino [AlBrNCH2CH2NH2]n, n = 1-4, 6 (In), and isomeric amido [AlBrNHCH2CH2NH] n, n = 1-3 (An), species. In all cases the amido isomers are 95-295 kJ mol-1 more stable compared to their imino counterpairs. Intramolecular donor-acceptor interactions play an important role in the stabilization of the structure. Possible pathways of the polymerization have also been explored. Although the generation of the oligomers via HBr elimination in the gas phase is predicted to be thermodynamically unfavorable, operation of such reactions in the condensed phase is feasible. Substitution of bromine by hydrogen makes H2 elimination reactions thermodynamically favorable. This opens a perspective for the synthesis of novel ladder-type oligomers with a continuous (AlN)n core supported by C2H4 balustrade and imino cages with C2H4 handles.

AB - The structures and stability of monomelic and oligomeric compounds resulting from the elimination of 2 mol of HBr from the AlBr3en complex have been studied theoretically at the B3LYP/LANL2DZ(d,p) level of theory. Two series of the ring and cage oligomer compounds were considered: imino [AlBrNCH2CH2NH2]n, n = 1-4, 6 (In), and isomeric amido [AlBrNHCH2CH2NH] n, n = 1-3 (An), species. In all cases the amido isomers are 95-295 kJ mol-1 more stable compared to their imino counterpairs. Intramolecular donor-acceptor interactions play an important role in the stabilization of the structure. Possible pathways of the polymerization have also been explored. Although the generation of the oligomers via HBr elimination in the gas phase is predicted to be thermodynamically unfavorable, operation of such reactions in the condensed phase is feasible. Substitution of bromine by hydrogen makes H2 elimination reactions thermodynamically favorable. This opens a perspective for the synthesis of novel ladder-type oligomers with a continuous (AlN)n core supported by C2H4 balustrade and imino cages with C2H4 handles.

UR - http://www.scopus.com/inward/record.url?scp=64849083551&partnerID=8YFLogxK

U2 - 10.1021/jp805904e

DO - 10.1021/jp805904e

M3 - Article

AN - SCOPUS:64849083551

VL - 113

SP - 3420

EP - 3426

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 14

ER -