TY - JOUR
T1 - The structure of oxo-bridged trinuclear ruthenium and iridium hexacarboxylates
AU - Almog, Orna
AU - Bino, Avi
AU - Garfinkel-Shweky, Diana
PY - 1993/11
Y1 - 1993/11
N2 - The reactions between ruthenium trichloride or iridium trichloride and carboxylic acids produce oxygen-centered triangular trinuclear complexes which are known as 'basic' carboxylates having the general formula [M3O(O2CR)6(H2O3]n+. Using ion-exchange chromatography, a variety of such complexes with different carboxylates and oxidation states were isolated and crystallized. The X-ray study of five compounds is reported. Compound 1, [Ru3O(O2CCH3)6(H2O)3]BF4·2H2O is monoclinic, space group P2/c with a=11.717(1), b=15.019(2), c=15.220(2) Å, β=92.27(3)°, V=2676(1) Å3 and Z=4. Compound 2, [Ru3O(O2CH)6(H2O)6]BF4·3H2O is orthorhombic, space group Pmn21 with a=11.362(1), b=6.676(1), c=14.447(2) Å, V=1096(1) Å3 and Z=2. Compound 3, [Ru3O(O2CCH3)6(H2O)3](ClO4)2·H2O is monoclinic, space group P21/n with a=17.226(2), b=15.532(2), c=11.117(1) Å, β=91.68(2)°, V=2973(1) Å3 and Z=4. Compound 4, [Ir3O(O2CCH3)6(H2O)3]BF4·4H2O is monoclinic space group I2/a with a=22.305(6), b=14.098(3), c=20.119(5) Å, β=103.10(5)°, V=6162(5) Å3 and Z=8. Compound 5, [Ir3O(O2CCH3)6(H2O)3](ClO3)1.667(ClO4)0.333 is rhombohedral, space group R3 with a=11.173(4), c=40.621(10) Å, V=4392(4) Å3 and Z=6. The structural parameters, such as MO (central) distances, for the M(III,III,III) and M(III,III,IV) systems are almost identical. This indicates that the removal of a d-electron from a non-bonding level of the M3O system has a very little or no effect at all on this system.
AB - The reactions between ruthenium trichloride or iridium trichloride and carboxylic acids produce oxygen-centered triangular trinuclear complexes which are known as 'basic' carboxylates having the general formula [M3O(O2CR)6(H2O3]n+. Using ion-exchange chromatography, a variety of such complexes with different carboxylates and oxidation states were isolated and crystallized. The X-ray study of five compounds is reported. Compound 1, [Ru3O(O2CCH3)6(H2O)3]BF4·2H2O is monoclinic, space group P2/c with a=11.717(1), b=15.019(2), c=15.220(2) Å, β=92.27(3)°, V=2676(1) Å3 and Z=4. Compound 2, [Ru3O(O2CH)6(H2O)6]BF4·3H2O is orthorhombic, space group Pmn21 with a=11.362(1), b=6.676(1), c=14.447(2) Å, V=1096(1) Å3 and Z=2. Compound 3, [Ru3O(O2CCH3)6(H2O)3](ClO4)2·H2O is monoclinic, space group P21/n with a=17.226(2), b=15.532(2), c=11.117(1) Å, β=91.68(2)°, V=2973(1) Å3 and Z=4. Compound 4, [Ir3O(O2CCH3)6(H2O)3]BF4·4H2O is monoclinic space group I2/a with a=22.305(6), b=14.098(3), c=20.119(5) Å, β=103.10(5)°, V=6162(5) Å3 and Z=8. Compound 5, [Ir3O(O2CCH3)6(H2O)3](ClO3)1.667(ClO4)0.333 is rhombohedral, space group R3 with a=11.173(4), c=40.621(10) Å, V=4392(4) Å3 and Z=6. The structural parameters, such as MO (central) distances, for the M(III,III,III) and M(III,III,IV) systems are almost identical. This indicates that the removal of a d-electron from a non-bonding level of the M3O system has a very little or no effect at all on this system.
UR - http://www.scopus.com/inward/record.url?scp=0001788934&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(00)83819-0
DO - 10.1016/S0020-1693(00)83819-0
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AN - SCOPUS:0001788934
SN - 0020-1693
VL - 213
SP - 99
EP - 102
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -