TY - JOUR
T1 - "True" inorganic heterocycles
T2 - Structures and stability of group 13-15 analogues of benzene and their dimers
AU - Timoshkin, Alexey Y.
AU - Frenking, Gernot
PY - 2003/1
Y1 - 2003/1
N2 - Group 13-15 inorganic analogues of benzene, [HMYH]3 (M = B, Al, Ga; Y = N, P, As), mixed heterocycles of the type [BAIGaNPAs]H6 and their dimers have been theoretically examined at the B3LYP/TZVP level of theory. Six different isomers have been structurally characterized for the mixed compounds [BAIGaNPAs]H6. B-N bonding strongly (about ∼90-100 kJ mol-1) stabilizes the mixed heterocycles, followed by the preference of the Al-N bonded structures over Ga-N bonded (∼30-40 kJ mol-1), while B-P bonding is slightly (5-10 kJ mol-1) more favorable compared to B-As. Thus, the B-N-Al-As-Ga-P bonding pattern is predicted to be the most stable, followed by the B-N-Al-P-Ga-As core. Processes of [HMYH]3 formation from donor-acceptor complexes H3MYH3 are predicted to be thermodynamically favorable for all MY combinations. Dimerization reactions of the coordinationally unsaturated [HMYH]3 heterocycles yielding hexamer clusters [HMYH]6 are found to be exothermic, with the exception of borazine, for which, as for benzene, dimerization is strongly endothermic due to the aromaticity of C6H6 and [HBNH]3. Despite the high endothermicity of [HBNH]3 dimerization, the B-N bond formation is the driving force of the dimerization of mixed species [BAIGaNPAs]H6. The dimerization enthalpies of [BAIGaNPAs]H6 may be both exo- and endothermic, depending on the bonding pattern of the isomers. A complete set of mean MY bond energies in four- and six-membered cycles of [HMYH]6 was derived. The MY energies were found to be transferable quantities and may serve for a qualitative prediction of the relative stability of different isomers of mixed cluster compounds. [BAIGaNPAs]2H12 clusters are promising synthetic targets, they are expected to serve as single-source precursors for the stoichiometry-controlled CVD processes of the group 13-15 composites. A strategy of their synthesis and the most suitable starting systems have been also predicted.
AB - Group 13-15 inorganic analogues of benzene, [HMYH]3 (M = B, Al, Ga; Y = N, P, As), mixed heterocycles of the type [BAIGaNPAs]H6 and their dimers have been theoretically examined at the B3LYP/TZVP level of theory. Six different isomers have been structurally characterized for the mixed compounds [BAIGaNPAs]H6. B-N bonding strongly (about ∼90-100 kJ mol-1) stabilizes the mixed heterocycles, followed by the preference of the Al-N bonded structures over Ga-N bonded (∼30-40 kJ mol-1), while B-P bonding is slightly (5-10 kJ mol-1) more favorable compared to B-As. Thus, the B-N-Al-As-Ga-P bonding pattern is predicted to be the most stable, followed by the B-N-Al-P-Ga-As core. Processes of [HMYH]3 formation from donor-acceptor complexes H3MYH3 are predicted to be thermodynamically favorable for all MY combinations. Dimerization reactions of the coordinationally unsaturated [HMYH]3 heterocycles yielding hexamer clusters [HMYH]6 are found to be exothermic, with the exception of borazine, for which, as for benzene, dimerization is strongly endothermic due to the aromaticity of C6H6 and [HBNH]3. Despite the high endothermicity of [HBNH]3 dimerization, the B-N bond formation is the driving force of the dimerization of mixed species [BAIGaNPAs]H6. The dimerization enthalpies of [BAIGaNPAs]H6 may be both exo- and endothermic, depending on the bonding pattern of the isomers. A complete set of mean MY bond energies in four- and six-membered cycles of [HMYH]6 was derived. The MY energies were found to be transferable quantities and may serve for a qualitative prediction of the relative stability of different isomers of mixed cluster compounds. [BAIGaNPAs]2H12 clusters are promising synthetic targets, they are expected to serve as single-source precursors for the stoichiometry-controlled CVD processes of the group 13-15 composites. A strategy of their synthesis and the most suitable starting systems have been also predicted.
UR - http://www.scopus.com/inward/record.url?scp=0037237278&partnerID=8YFLogxK
U2 - 10.1021/ic020361a
DO - 10.1021/ic020361a
M3 - 文章
C2 - 12513078
AN - SCOPUS:0037237278
SN - 0020-1669
VL - 42
SP - 60
EP - 69
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -