For a long time, planar tetracoordinate carbon (ptC)
represented
an exotic coordination mode in organic and organometallic chemistry,
but it is now a useful synthetic building block. In contrast, realization
of planar tetracoordinate silicon (ptSi), a heavier analogue of ptC,
is still challenging. Herein we report the successful synthesis and
unusual reactivity of the first ptSi species of divalent silicon present
in 3, supported by the chelating bis(N-heterocyclic silylene)bipyridine ligand, 2,2′-{[(4-tBuPh)C(N
t
Bu)]2SiNMe}2(C5N)2, 1]. The compound
resulted from direct reaction of 1 with Idipp-SiI2 [Idipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene].
Alternatively, it can also be synthesized by a two-electron reduction
of the corresponding Si(IV) precursor 2 with 2 molar
equiv of KC10H8. Density functional theory calculations
show that the lone pair at the ptSi(II) resides almost completely
in its 3p
z
orbital, very
different from known four-coordinate silylenes. Oxidative addition
of MeI to the ptSi(II) atom affords the corresponding pentacoordinate
Si(IV) compound 4, with the methyl group located in an
apical position. Remarkably, the reaction of 2 with [CuO
t
Bu] leads to the regeneration of the bis(silylene)
arms via Si–Si bond scission and induces the Si(II) →
Si(IV) oxidation of the central Si(II) atom and concomitant two-electron
reduction of the bipyridine moiety to form the neutral bis(silylene)silyl
Cu(I) complex 5.