A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone
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In: Angewandte Chemie Volume 60 / Issue 5 (2020-10-15) , S. 2624-2628; eissn:1521-3773
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The N-heterocyclic silylene [{Fe(η⁵-C₅H4-NDipp)₂}Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO₂ and N₂O, respectively affording (1DippSiO₂)₂C and (1DippSiO)₂ as follow-up products of the silanone 1DippSiO. Its reactions with H₂O, NH₃, and FcPH₂ (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH₂, PHFc). Its reaction with H₃BNH₃ unexpectedly results in B−H, instead of N−H, bond activation, affording 1DippSi(H)(BH₂NH₃). DFT results suggest that dramatically different mechanisms are operative for these H−X insertions.
@article{doi:10.17170/kobra-202107204382, author ={Weyer, Nadine and Heinz, Myron and Schweizer, Julia Isabella and Bruhn, Clemens and Holthausen, Max C. and Siemeling, Ulrich}, title ={A Stable N-Heterocyclic Silylene with a 1,1′-Ferrocenediyl Backbone}, keywords ={540 and Carbene and Einschiebungsreaktion and Metallocene and Silicium and Valenz }, copyright ={http://creativecommons.org/licenses/by/4.0/}, language ={en}, journal ={Angewandte Chemie}, year ={2020-10-15} }