SPECTROSCOPIC, MAGNETIC AND STRUCTURAL STUDIES ON THE MIXED-VALENCE CUBOIDAL CLUSTERS [MO(4)E(4)(EDTA)(2)](3-) (E=S OR SE, H(4)EDTA=ETHYLENEDIAMINETETRAACETIC ACID) AND [MO4S4(H2O)(12)](5+)
W. Mcfarlane et al., SPECTROSCOPIC, MAGNETIC AND STRUCTURAL STUDIES ON THE MIXED-VALENCE CUBOIDAL CLUSTERS [MO(4)E(4)(EDTA)(2)](3-) (E=S OR SE, H(4)EDTA=ETHYLENEDIAMINETETRAACETIC ACID) AND [MO4S4(H2O)(12)](5+), Journal of the Chemical Society. Dalton transactions, (3), 1996, pp. 363-369
The Se-77 NMR spectrum of the mixed-valence cluster [Mo4Se4(edta)(2)](
3-) (H(4)edta = ethylenediamine-N,N,N',N'-tetraacetic acid) was record
ed and appears to be consistent with the presence in solution of a val
ence-trapped species (Mo3MoIV)-Mo-III with a lifetime in excess of 10(
-5) s. However this was not supported by Mo-95 and Se-77 NMR studies o
n other [Mo4Se4(edta)(2)](n-) (n = 2 or 4) clusters. Overall it appear
s that multiple NMR signals arise from the presence in solution of spe
cies which differ slightly from the above formulae in the extent of co
-ordination of H2O and edta. The studies do not preclude the possibili
ty of valence-trapped species with lifetimes shorter than 10(-6) s. A
model in which intervalence electron exchange within the core clusters
Mo(4)E(4)(5+) (E = S or Se) is slower than formation/decay (approxima
te to 10(9) s(-1)) of ion-pair precursors is proposed to account for t
he biphasic kinetic behaviour previously observed for substitution of
H2O on [Mo4S4(H2O>(12)](5+) The crystal structure of a hydrated sodium
salt of [Mo4Se4(edta)(2)](3-) has been determined, and is compared to
that previously obtained for [Mo4S4(edta)(2)](3-). Other techniques e
xplored include magnetic moment measurements on a solid sample of [Mo4
S4(H2O)(12)][pts](5) . 14H(2)O (pts = toluene-p-sulfonate) which show
a Curie-like behaviour (chi = C/T) for an S = 1/2 ground state, with a
corresponding magnetic moment independent of temperature over the ran
ge 300-4.2 K. Metal-ligand stretching frequencies from Fourier-transfo
rm IR studies on the chloride salt of the same 5+ cluster have also be
en obtained.