SYNTHESIS, STRUCTURES, AND SPECTROSCOPIC, MAGNETIC, AND ELECTROCHEMICAL PROPERTIES OF (MU-ALKOXO)BIS(MU-CARBOXYLATO)DIRUTHENIUM COMPLEXES, M[RU-2(DHPTA)(MU-O(2)CR)(2)] (M=NA AND K, DHPTAH(5)=1,3-DIAMINO-2-HYDROXYPROPANETETRAACETIC ACID)
T. Tanase et al., SYNTHESIS, STRUCTURES, AND SPECTROSCOPIC, MAGNETIC, AND ELECTROCHEMICAL PROPERTIES OF (MU-ALKOXO)BIS(MU-CARBOXYLATO)DIRUTHENIUM COMPLEXES, M[RU-2(DHPTA)(MU-O(2)CR)(2)] (M=NA AND K, DHPTAH(5)=1,3-DIAMINO-2-HYDROXYPROPANETETRAACETIC ACID), Inorganic chemistry, 35(21), 1996, pp. 6230-6239
[RuCl2(dmso)(4)] (dmso = dimethyl sulfoxide) was treated with dhptaH(5
) (1,3-diamino-2-hydroxypropanetetraacetic acid) and carboxylate ligan
ds in the presence of NaOH or KOH and gave dinuclear ruthenium(III) co
mplexes of dhpta with two bridging carboxylates, M[Ru(dhpta)(mu-O(2)CR
)(2)] (1, R = C6H5, M = Na; 1', R = C6H5, M = K; 2, R = p-OHC6H4, M =
Na; 3, R = p-NH2C6H4, M = Na; 4, R = CH3, M = Na; 4', R = CH3, M = K),
which were characterized by elemental analysis, mass, electronic abso
rption, and H-1 and C-13 NMR spectroscopies, and X-ray absorption and
crystallographic analyses (4, orthorhombic, space group Pca2(1) with a
= 21.359(4) Angstrom, b = 7.484(2) Angstrom, c = 12.930(2) Angstrom,
Z = 4, R = 0.065, and R(w) = 0.044 for 1116 independent reflections wi
th I > 3 sigma(I); 4'. 1.5H(2)O: monoclinic, P2(1), a = 7.689(2) Angst
rom, b = 17.213(2) Angstrom, c = 18.103(2) Angstrom, beta = 94.50(1)de
grees, Z = 4; R = 0.041, and R(w) = 0.047 for 4705 independent reflect
ions with I > 3 sigma(I)). The complex anion consists of two ruthenium
atoms bridged by the alkoxide of dhpta and the two acetate ligands. T
he Ru-Ru distances of 3.433(3) Angstrom (4) and 3.421(1) Angstrom (ave
rage) (4') are longer than those found in (mu-oxo)bis(mu-carboxylato)d
iruthenium(III) complexes. EXAFS analysis and H-1 NMR spectra indicate
d that complexes 1-4 have the identical dinuclear structure in both so
lid and water solution states. Temperature-dependent magnetic suscepti
bility of 1-4 showed a strong antiferromagnetic interaction between th
e two Ru(III) ions with -J = 310-470 cm(-1). Cyclic voltammograms show
ed two reduction processes at ca. -0.34 and ca. -0.94 V vs Ag/AgCl, co
rresponding to two stepwise one-electron reductions, (RuRuIII)-Ru-III
<-> (RuRuII)-Ru-III <-> (RuRuII)-Ru-II. The most remarkable feature is
the large separation between the two redox potentials, implying that
the mixed-valence diruthenium(III,II) complexes of dhpta are fairly st
able. Potentiostatic electrolysis of 1-4 at a potential in between E(1
/2)(1) and E(1/2)(2) consumed 1 F per dimer and afforded a mixed-valen
ce diruthenium species, [(RuRuIII)-Ru-II(dhpta)mu-O(2)CR)(2)](2-), in
solution, which showed two weak and broad absorption bands (nu(max) 5.
5-5.7 and 11.6-11.9 kcm(-1)) in DMF assignable to intervalence charge
transfer (IT) bands. The lower energy IT band was analyzed by Gaussian
curve fitting and the electron exchange integral H-ad was estimated a
s 640-870 cm(-1) on the basis of Hush's theory. The spectroscopic anal
ysis indicated that [(RuRuIII)-Ru-II(dhpta)(O(2)CR)(2)](2-) belongs to
Class II type mixed-valence diruthenium complexes.