Extended Hypervalent 5c-6e Interactions
SCHEME 1. Ap p r oxim a te Molecu la r Or bita l
Mod el of Z5 5c-6e
To reveal the nature of 5c-6e is the next extension of
our investigations on the extended hypervalent mc-ne
(m g 4). 5c-6e are the σ-type linear bonds constructed
by five atoms with six electrons, of which an approximate
molecular model is shown in Scheme 1. How can 5c-6e
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be constructed? Our strategy is to employ the nonbonded
interactions containing lone pairs. Lone-pair orbitals
interact with others when they approach nearby and
various types of charge-transfer (CT) will contribute to
the nonbonded interactions containing lone pairs. Al-
though the interactions are usually repulsive, they
become attractive if all orbitals taking part in the
interactions are not filled with electrons. CT from lone
pairs to acceptors is accompanied by the attractive
interactions. The driving force for the formation of
X-Z-X 3c-4e is CT from the central atom Z to the
outside atoms X, resulting in the highly polar Xδ--Zδ+
-
Xδ- bonds.2c,9,10 That of X- - -Z-Z- - -X 4c-6e is CT from
outside atoms X to the central σ*(Z-Z), which forms polar
X
δ+- - -Zδ--Zδ-- - -Xδ+ bonds.2a-f,11 The direction of CT in
4c-6e is just the opposite to that in 3c-4e. They are
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-
typical examples of the interactions. The bonds in Br5
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-
structures seem more stable than the linear ones for Br5
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