Four different mechanisms and the effect of bulky groups were studied in the reaction of ({HC[CMeN(R)]2}Si, R = 2,6-diisopropylphenyl) with white phosphorus. The carefully tested B3LYP-D, ωB97X-D, and SOS-MP2 methods, by the CCSD(T) method, with cc-pVTZ basis set provided consonant results which support the reliability of our results and the applicability of these methods. The dispersion energy...

Full quantum chemical calculations with density functional theory (DFT) show that bond-strengthening back-donation to a π-diborene, recently discovered for transition metal systems (Braunschweig and co-workers, Nat. Chem., 2013, 5, 115-121), would be just as favored for Main Group silylene complexes. This result not only shows the range and applicability of the bond-strengthening back-bonding i...

Recently, the chemistry of element (0) compounds has attracted the attention of both experimental and theoretical chemists. In this article, some new Si(0) and Ge(0) compounds stabilized by different silylene and germylene ligands are studied theoretically by applying quantum chemical calculations and topography mapping of molecular electrostatic potential (MESP). These compounds are found to h...

With the aim of recognizing the steric effects on the silylenic R2C6H6Si structures, DFT calculationsare carried out on 8 structures of R2C6H6Si (where R is hydrogen (H), methyl (Me), isopropyl (i-pro),and tert-butyl (tert-Bu)). These species are at either triplet (t) or singlet (s) states. Singlet–tripletenergy separations ( Me (20.32) > t-Bu (15.92).all singlet states of R2C6H6Si, are more st...

Open AccessCCS ChemistryCOMMUNICATION6 Jun 2022Forging a Cage into Chain: Stepwise Transformation of P4 by Silylenes to Si3P4 Motif Xiaofei Sun, Alexander Hinz and Peter W. Roesky Sun Institute Inorganic Chemistry, Karlsruhe Technology (KIT), 76131 Google Scholar More articles this author , *Corresponding author: E-mail Address: [email protected] https://doi.org/10.31635/ccschem.022.202101709 S...

The challenge motivating this paper is to induce, by chemical substitution, a silylyne, SiR, or a congeneric carbyne, CR, to adopt the high-spin quartet rather than the low-spin doublet as its ground state. The difficulty is seen in the preference for the doublet of the parent SiH (doublet-quartet energy difference ∼39 kcal/mol, favoring the doublet) or CH (∼17 kcal/mol). Strategies for having ...

Time-resolved studies of the title reactions have been carried out over the pressure range 1−100 Torr (in SF6 bath gas) and at temperatures in the range 293−600 K, using laser flash photolysis techniques to generate and monitor the silylenes, SiH2 and SiMe2. All three reactions showed evidence of pressure dependence, consistent with third-body assisted association reactions to form silirane pro...

Reaction of different combinations of aryl(dihalo)boranes and trialkylsilyl iron metallates, a route previously used to prepare a terminal iron arylborylene complex, is found to lead to three distinct new reaction outcomes, including unselective decomposition, an inert iron(II) (boryl)(silyl) complex, and a dinuclear bis(μ-silylene) complex. The latter result is to our knowledge the first examp...