Activation of 7‑Silanorbornadienes by N‑Heterocyclic Carbenes: A Selective Way to N‑Heterocyclic-Carbene-Stabilized Silylenes Dennis Lutters Claudia Severin Marc Schmidtmann Thomas Müller 10.1021/jacs.6b02824.s006 https://acs.figshare.com/articles/dataset/Activation_of_7_Silanorbornadienes_by_N_Heterocyclic_Carbenes_A_Selective_Way_to_N_Heterocyclic_Carbene_Stabilized_Silylenes/3203989 The synthesis of hydridosilylenes Ter­(H)­Si: <b>3a</b> (Ter: 2,6-bis­(2,4,6-trimethylphenyl)­phenyl) and Ter*­(H)­Si: <b>3b</b> (Ter*: 2,6-bis­(2,4,6-tri<i>iso-</i>propylphenyl)­phenyl) stabilized by the N-heterocyclic carbene (NHC) ImMe<sub>4</sub> is reported. The synthesis of stabilized hydridosilylenes <b>3</b> was accomplished by a previously unknown NHC-induced fragmentation of silanorbornadiene derivatives. Structural studies of the stabilized silylenes <b>3</b> and of its Fe­(CO)<sub>4</sub> complex <b>12</b> accompanied by a theoretical analysis of their bonding situation indicate that stabilized silylenes such as <b>3</b> can be regarded as neutral silyl anion equivalents. A computational investigation of the reaction course indicate a virtual one-step reaction between the NHC and the silanorbornadiene. A theoretical assessment of the scope and limitations of this reaction suggests that it is general and can be used also for the synthesis of other carbene analogues such as germylenes and phosphinidenes. 2016-04-27 18:20:12 silylenes 3 Structural studies NHC hydridosilylenes 3 ImMe 4 synthesis reaction course bi silanorbornadiene derivatives silyl anion equivalents carbene analogues Selective Way Ter