0000000000107789
AUTHOR
Brian Rekken
showing 2 related works from this author
Isolation of a Stable, Acyclic, Two-Coordinate Silylene
2012
The synthesis and characterization of a stable, acyclic two-coordinate silylene, Si(SArMe6)2, (ArMe6 = C6H3-2,6(C6H2-2,4,6-Me3)2) by reduction of Br2Si(SArMe6)2 with a magnesium(I) reductant is described. It features a v-shaped silicon coordination with a S-Si-S angle of 90.519(2)° and an average Si-S distance of 2.158(3) Å. Although it reacts readily with an alkyl halide, it does not react with hydrogen under ambient conditions probably as a result of the ca. 4.3 eV energy difference between the frontier silicon lone pair and 3p orbitals. peerReviewed
Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si-Pb) Dichalcogenolate Carbene Analogues with Sub-9…
2013
The synthesis and 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, including two new acyclic silylenes) 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 found to become narrower as the size of the ligand was increased. Experimental and structural data in conjunction with high-level DFT calculations, in…