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Bonding analysis; Dative bonds; Disilenes; Silylenes; X-ray diffraction
Abstract:
An experimental and theoretical study of the base-
stabilized disilene 1 is reported, whichforms at lowtemper-
atures in the disproportionation reaction of Si
2
Cl
6
or neo-
Si
5
Cl
12
with equimolar amounts of NMe
2
Et. Single-crystal X-
ray diffraction and quantum-chemical bonding analysis dis-
close an unprecedented structure in silicon chemistry featuring
adative Si!Si single bond between two silylene moieties,
Me
2
EtN!SiCl
2
!Si(SiCl
3
)
2
.The central ambiphilic SiCl
2
group is linked by dative bonds to the amine donor and the
bis(trichlorosilyl)silylene acceptor,which leads to push–pull
stabilization. Based on experimental and theoretical examina-
tions aformation mechanism is presented that involves an
autocatalytic reaction of the intermediately formed anion
Si(SiCl
3
)
3
¢
with neo-Si
5
Cl
12
to yield 1.
