A Stable Magnesium Bromosilylenoid: Transmetalation of a Lithium Bromosilylenoid by Magnesium Bromide

Lim, Young Mook; Cho, Hyeon Mo; Lee, Myong Euy; Baeck, Kyoung Koo

doi:10.1021/om060589w

Cited by 29 publications

(16 citation statements)

References 25 publications

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“…Instead, the dibromo-bisthiolato Si(IV) Si NMR spectrum. 30 The upfield shift of SiBr(MgBr)(SAr Me 6 )2 is probably due to the more electronegative thiolate substituents. The silylenoid is likely an intermediate in the synthesis of silylenes 2 and 3; however, in those systems, the MgBr2 is apparently eliminated, possibly due to increased steric crowding of the bulkier ligands (Supporting Information).…”

Section: Computational Detailsmentioning

confidence: 99%

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

et al. 2013

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The synthesis, spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand, Ch-M-Ch, bond angles that are often well below 90°.Furthermore, and contrary to normal steric expectations, the interligand angles were 2 found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, including corrections for dispersion effects, led to the conclusion that dispersion forces play a key role in stabilizing their acute interligand angles.

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Section: Computational Detailsmentioning

confidence: 99%

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

et al. 2013

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“…In 1996, Ohtaki and Ando described the synthesis of at risyl-substituted chlorogermylenoid (Figure 1, IV;T si = (Me 3 Si) 3 C), [6] however,t he molecular structure of this compound in the solid state was not reported. [8] In contrast, the field of heavier Group 14 congeners (containing Sn or Pb) remains largely unexplored mainly as aresult of the increased stability of the divalent Sn II and Pb II atoms in comparison to the lighter elements. [7] In this context, reactivity studies on silylenoids by Lee and co-workers have to be pointed out.…”

mentioning

confidence: 99%

A Tin Analogue of Carbenoid: Isolation and Reactivity of a Lithium Bis(imidazolin‐2‐imino)stannylenoid

Ochiai

Franz

et al. 2016

Angewandte Chemie

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The lithium bis(imino)stannylenoid (NIPr) 2 Sn-(Li)Cl (1;N IPr = bis(2,6-diisopropylphenyl)imidazolin-2-imino) was prepared by the reaction of LiNIPr with 0.5 equiv of SnCl 2 ·diox( diox = 1,4-dioxane) and the ambiphilic character of the compound was demonstrated by investigations into its reactivity.T reatment of 1 with I 2 or MeI yielded the oxidative addition products (NIPr) 2 SnI 2 and (NIPr) 2 Sn(Me)I, respectively.I nc ontrast, the reaction of 1 with one equivalent of Me 3 SiCl resulted in the formation of Me 3 SiNIPr and the chlorostannylene dimer [NIPrSnCl] 2 . Moreover,t he substitution reaction of compound 1 with MeLi led to the formation of the methyl-substituted stannate (NIPr) 2 Sn(Li)Me.

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“…On the other hand, since Clark et al [37] studied the isomers of lithoflurosilylenoid H 2 SiLiF theoretically using ab initio calculations for the first time in 1980, many silylenoids such as R 1 R 2 SiMX (R 1 , R 2 =H, F, OH, NH 2 , Me, Et; M=Li, Na, K, Be, Mg, etc. ; X=F, Cl, Br) [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] have been investigated by quantum chemistry methods. Such theoretical studies show that R 1 R 2 SiMX has four possible structures (see Scheme 1): a p-complex (I), a three-membered-ring (ii), an σ-complex (iii), and a 'classical' tetrahedral (iv).…”

Section: Introductionmentioning

confidence: 99%

Insight into the substitution reactions of silylenoid H2SiLiF with GeH3X (X = F, Cl, Br): a theoretical study

Yan

Xiao

et al. 2015

J Mol Model

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The unique substitution reactions of the three-membered-ring silylenoid H2SiLiF with GeH3X (X = F, Cl, Br) were investigated using ab initio and density functional theory calculations. All stationary points on the potential energy surfaces were optimized at the B3LYP/6-311 + G (d, p) level of theory and the QCISD method was then used to calculate the single-point energies. Theoretical calculations predicted that the substitution reactions of H2SiLiF with GeH3X proceed via two reaction paths (I and II), while forming the same product H2FSi-GeH3. In either pathway, there is one precursor complex (Q), one transition state (TS), and one intermediate (IM) connecting the reactants and products. The substitution reaction barriers of H2SiLiF with GeH3X for path I (48.49, 42.71, and 38.71 kJ mol(-1)) decreased with the increase for the same-family element X from up to down in the periodic table, whereas the substitution barriers for path II (6.51, 22.04, and 23.62 kJ mol(-1)) increased with the increase in atomic number of X (X = F, Cl, Br). Path II was more favorable than path I. All the substitution reactions of H2SiLiF with GeH3X were exothermic. The elucidation of the unique mechanism of these substitution reactions suggests a new reaction mode of silicon-germanium bond formation.

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A Stable Magnesium Bromosilylenoid: Transmetalation of a Lithium Bromosilylenoid by Magnesium Bromide

Cited by 29 publications

References 25 publications

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

A Tin Analogue of Carbenoid: Isolation and Reactivity of a Lithium Bis(imidazolin‐2‐imino)stannylenoid

Insight into the substitution reactions of silylenoid H2SiLiF with GeH3X (X = F, Cl, Br): a theoretical study

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