The relationship between molecular and crystal structures of
organometallic complexes showing intermolecular
interactions of the M−H- - -H−M and M−H- - -H−C type has
been investigated by a combined use of extended
Hückel and DFT calculations, and crystal packing analysis.
Molecular and crystal structures determined by
neutron
and/or X-ray diffraction experiments of coordination complexes and
clusters showing intermolecular
M−H- - -H−M and M−H- - -H−C interactions below 2.6 Å have
been retrieved from the Cambridge Structural
Database. Molecular orbital analysis has been carried out by means
of extended Hückel and DFT calculations on
selected compounds. For the HMn(CO)5 dimer, where
the interaction is of the M−H- - -H−M type, the
system
is reminiscent of a bound hydrogen molecule where the H−H bond has
been greatly weakened. A very small
binding energy of ca. 5 kJ mol-1 has been
determined using DFT calculations. This simple interpretation
does
not hold in the cases of M−H- - -H−C short contacts, which are
more appropriately described as arising from a
special type of hydrogen bond associated with opposite charges on the
two hydrogen atoms.
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