TY - JOUR
T1 - Estimating the stability and reactivity of acyclic and cyclic mono-heteroatom substituted germylenes
T2 - A density functional theory investigation
AU - Sojoudi, A.
AU - Shakib, F. A.
AU - Momeni, M. R.
AU - Imani, M.
AU - Shojaee, S.
PY - 2013/4/1
Y1 - 2013/4/1
N2 - DFT computations coupled with appropriate isodesmic reactions are employed to investigate the effects of mono-heteroatom substitution, cyclization and unsaturation on the stability, multiplicity and reactivity of amino-, oxy-, silyl-, phosphino-, and thioalkylgermylenes. The results are based on the references to the parent symmetrical acyclic, saturated/unsaturated cyclic dialkylgermylenes. The calculated singlet-triplet energy gaps (ΔES-T) demonstrate the following trend: (amino≈oxy)>thio>alkyl>phosphino>silyl. Cyclization increases the ΔES-T of the all germylenes, but unsaturation considerably decreases it. Isodesmic reactions show that π-donor/σ-acceptor amino, oxy and thio stabilize both singlet and triplet germylenes but with a more considerable effect on the former while phosphino acts reversely. The reactivity of the species is discussed in terms of nucleophilicity, electrophilicity and proton affinity issues showing silyl and phosphinoalkylgermylenes more nucleophilic and more basic than amino and oxyalkylgermylenes.
AB - DFT computations coupled with appropriate isodesmic reactions are employed to investigate the effects of mono-heteroatom substitution, cyclization and unsaturation on the stability, multiplicity and reactivity of amino-, oxy-, silyl-, phosphino-, and thioalkylgermylenes. The results are based on the references to the parent symmetrical acyclic, saturated/unsaturated cyclic dialkylgermylenes. The calculated singlet-triplet energy gaps (ΔES-T) demonstrate the following trend: (amino≈oxy)>thio>alkyl>phosphino>silyl. Cyclization increases the ΔES-T of the all germylenes, but unsaturation considerably decreases it. Isodesmic reactions show that π-donor/σ-acceptor amino, oxy and thio stabilize both singlet and triplet germylenes but with a more considerable effect on the former while phosphino acts reversely. The reactivity of the species is discussed in terms of nucleophilicity, electrophilicity and proton affinity issues showing silyl and phosphinoalkylgermylenes more nucleophilic and more basic than amino and oxyalkylgermylenes.
KW - Density functional theory
KW - Electronic structure
KW - Ionization energy
KW - Isodesmic reaction
KW - Stable germylenes
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U2 - 10.1016/j.comptc.2013.01.001
DO - 10.1016/j.comptc.2013.01.001
M3 - Article
AN - SCOPUS:84873604393
SN - 2210-271X
VL - 1009
SP - 81
EP - 85
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -