Reactions of Stable Amidinate Chlorosilylene and [1+4]‐Oxidative Addition of N‐Heterocyclic Silylene with N ‐Benzylideneaniline

The reaction of PhC(N t Bu) 2 SiCl ( L ) with N 2 O afforded the trimer {PhC(N t Bu) 2 Si(O)Cl} 3 ( 1 ), which contains a Si 3 O 3 six‐membered ring. In the molecular structure of 1 , the PhC(N t Bu) 2 moieties are arranged around the Si 3 O 3 six‐membered ring in a paddle‐wheel fashion. Further the reaction of L with B(C 6 F 5 ) 3 and 9‐BBN (9‐borobicyclo[3.3.1]nonane) yielded the chlorosilylene–boron adducts L· B(C 6 F 5 ) 3 ( 2 ) and L· 9‐BBN ( 3 ). The reaction of CH{(C=CH 2 )(CMe)(2,6‐ i Pr 2 C 6 H 3 N) 2 }Si ( L′ ) with N ‐benzylideneaniline resulted in 4 , a [1+4]‐ rather than a [1+2]‐cycloaddition product. Compounds 1 – 4 were characterized by elemental analyses and spectroscopic methods. The molecular structures of 1 , 2 , and 4 were established unequivocally by single‐crystal X‐ray structural analysis. The formation of products 1 and 4 was supported by DFT calculations.