A Remarkable End-On Activation of Diazoalkane and Cleavage of Both C–Cl Bonds of Dichloromethane with a Silylene to a Single Product with Five-Coordinate Silicon Atoms

The 1:1 reaction of benzamidinato-stabilized chlorosilylene
PhC­(NtBu)2SiCl (1) with CH­(SiMe3)­N2 resulted in the formation of colorless [PhC­(NtBu)2Si­(Cl)­{N2CH­(SiMe3)}]2 (2), which consists of a four-membered Si2N2 ring. Surprisingly, N2 elimination
from the diazoalkane did not occur, but rather an end-on activation
of the nitrogen was observed. For the mechanism, we propose the formation of a silaimine
complex A as an intermediate, which is formed during
the reaction and dimerized under [2 + 2] cycloaddition to 2. In contrast, treatment of 1 with dichloromethane afforded
a 2:1 product, [{PhC­(NtBu)2Si­(Cl2)}2CH2] (3), which is obviously
formed by oxidative addition under cleavage of both C–Cl bonds
and formation of two Si–Cl and two Si–C bonds. Both
silicon atoms in 3 are five-coordinate. Compounds 2 and 3 were characterized by single-crystal
X-ray studies, multinuclear NMR spectroscopy, and EI-mass spectrometry.