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

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• 作者：Brian D. Rekken ; Thomas M. Brown ; James C. Fettinger ; Felicitas Lips ; Heikki M. Tuononen ; Rolfe H. Herber ; Philip P. Power
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 10, 2013
• 年：2013
• 卷：135
• 期：27
• 页码：10134-10148
• 全文大小：669K
• 年卷期：v.135,no.27(July 10, 2013)
• ISSN：1520-5126

文摘

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鈥攖he most notable of which is their strong tendency to display acute interligand, Ch鈥揗鈥揅h, bond angles that are often well below 90掳. 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, including corrections for dispersion effects, led to the conclusion that dispersion forces play an important role in stabilizing their acute interligand angles.