Mechanistic investigation of the reactivity of disilene with nitrous oxide: A DFT study

Computational Investigation on the Role of Disilene Substituents Toward N2O Activation

“…From the above findings it is worthwhile to note that the lone pair donor substituents exhibit antagonist influence on the reaction steps: on one hand it accelerates the I X t → S X dissociation whereas on the other hand it retards the S A + N 2 O → 1 A step. However, in our parent silylene S (Scheme ) the N lone pair is no longer delocalized toward the Si center, because the filled orbital remains orthogonal to the vacant p-orbital on Si, mostly due to the steric bulk from TMS group . In that case the silylene moiety is stabilized by the augmentation of coordination number on silicon center by the −Cp* group.…”

“…Herein, the fundamental steps involve in Pathway I are described for S A (Figure ) whereas for other analogues ( S B–F,R ) they are collected in the Supporting Information (Figures S2–S7). According to our previous report the terminal N atom of N 2 O binds to the silylene S leading to a stable intermediate 1 , as displayed in Scheme . In search of a similar S → 1 step, the N 2 O was allowed to react with the silylene S A , leading to the transition state [S A -1 A ] ‡ , accompanied by an activation barrier of 29.0 kcal/mol (Figure ).…”

“…According to our previous report the terminal N atom of N 2 O binds to the silylene S leading to a stable intermediate 1, as displayed in Scheme 2. 60 In search of a similar S → 1 step, the N 2 O was allowed to react with the silylene S A , leading to the transition state [S A -1 A ] ‡ , accompanied by an activation barrier of 29.0 kcal/mol (Figure 5). The imaginary eigenmode corresponds to the incoming motion of terminal atoms (N and O) to the Si center.…”

Computational Exploration of Mechanistic Avenues in Metal‐Free CO2 Reduction to CO by Disilyne Bisphosphine Adduct and Phosphonium Silaylide

“…Hence, the possibility of forming the transient oxadisilirene derivative ( INT‐B ; Scheme 2) in the reaction medium can be discarded [21] . The generation of similar oxadisilirene intermediate was recently theoretically predicted during the computational investigation of disilene‐mediated N 2 O activation by our group [14l,m] . NBO analysis suggests the presence of a sp 0.39 hybridized lone pair on each of the silicon centers in the disiloxane intermediate INT‐5 with an occupancy of 1.933 e .…”

Discriminate between Antibacterial and Non-Antibacterial Drugs Artificial Neutral Networks of a Multilayer Perceptron (MLP) Type Using a Set of Topological Descriptors

“…On the other hand, heavy metal toxicity and diseases represent class of natural compounds which Carbene (CH 2 ), Silylene (SiH 2 ), Germylene (GeH 2 ), Tin Dihydride (SnH 2 ), Lead (II) Hydride and Plumbous Hydride (PbH 2 ) are some of them. Highly reactive intermediates, Carbene (CH 2 ), Silylene (SiH 2 ), Germylene (GeH 2 ), Tin Dihydride (SnH 2 ), Lead (II) Hydride and Plumbous Hydride (PbH 2 ) have attracted much attention in organic, inorganic and physical chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. Full geometry optimizations are carried out on singlet and triplet states of alkyl substituted Acylic Carbene (CH 2 ), Acylic Silylene (SiH 2 ), Acylic Germylene (GeH 2 ), Acylic Tin Dihydride (SnH 2 ), Acylic Lead (II) Hydride and Plumbous Hydride (PbH2) by HF, PM3, MM2, MM3, AM1, MP2, MP3, MP4, CCSD, CCSD(T), LDA, BVWN, BLYP and B3LYP methods using 31G, 6-31G * , 6-31+G * , 6-31G(3df, 3pd), 6-311G, 6-311G * and 6-311+G * basis sets of the Gaussian 09.…”