P. Macchi et al., SITE PREFERENCE OF LIGAND AND METAL SUBSTITUTION IN TRIGONAL-BIPYRAMIDAL METAL-CARBONYL CLUSTERS, Organometallics, 16(10), 1997, pp. 2101-2109
Gimarc's topological charge stabilization rule (TCS), for addressing s
ite preference, has been extended to the realm of metal carbonyl clust
ers using Alien's energy indexes (EIs) instead of charges. EIs have be
en computed within the extended Huckel (EH) approximation and, in orde
r to assess an internal electronegativity scale for transition metals
and to allow comparisons across the periodic table, a homogeneous set
of EH parameters has been determined. EIs have been shown to behave si
milarly to charges on ''clusters'' with a rigid ligand stereochemistry
like carboranes but, when one deals with metal carbonyl clusters and
their intriguing ligand mobility, EIs are definitely superior to charg
es. EIs do address both ''skeletal'' and ''ligand'' site preferences a
ccording to the following rules of thumb: (i) more electronegative met
al atoms occupy higher EI sites of the uniform reference frame (URF) (
i.e. the one with the lower local electronegativity) and (ii) (nucleop
hilic) ligand substitution preferentially occurs on the lowest energy
index site of the URF (i.e. the one with the largest electrophilic cha
racter). Previous attempts to rationalize site preference in metal clu
sters were mainly concerned with the relative strengths of metal-metal
and metal-ligand bonds and substantially disregarded electronegativit
y differences between different metal atoms. In contrast, we have show
n that the latter are important whenever the actual URF allows for dif
ferent EIs on different metal sites. In particular, differences in ele
ctronegativity have been shown to be important for M5L15 and M5L14 but
not for M5L12 bipyramidal metal carbonyl clusters.