TY - JOUR
T1 - Triangular Trinuclear Molybdenum(IV) Cluster Compounds with Two Capping Oxygen Atoms
AU - Ardon, Michael
AU - Bino, Avi
AU - Cotton, F. Albert
AU - Dori, Zvi
AU - Kaftory, Menachem
AU - Reisner, George
PY - 1982
Y1 - 1982
N2 - The preparation and structural characterization of two trinuclear molybdenum(IV) cluster compounds with capping oxygen atoms are reported. Reaction of Mo(CO)6 with acetic acid under O2 allows the isolation, after suitable workup by cation-exchange resin chromatography of 1, [Mo3O2(OAc)6(H2O)3]Br2-H2O. This forms rhombohedral crystals in space group R3̄m with unit cell dimensions a = 11.784 (5) Å, a = 106.34 (5)°, V= 1386.6 (1) Å3, and Z = 2. The structure consists of [Mo3O2(O2CCH3)6(H2O)3]2+ ions having effectively D3h symmetry residing on crystallographic positions of C3v symmetry. The metal atoms form an equilateral triangle capped above and below by oxygen atoms. The edges of the triangle are each bridged by two acetate ions, and there is a water molecule coordinated to each metal atom with the Mo-OH2 bond direction intersecting the center of the opposite Mo-Mo bond. The bromide ions and the additional H2O are disordered over several positions in the rhombohedral cell. Reaction of Mo2(O2CCH3)4 with a mixture of propionic acid and propionic anhydride followed by cation column chromatography using CF3SO3H to elute gives [Mo3O2(O2C-C2H5)6(H2O)3](CF3SO3)2(CF3SO3H)(H2O)4. This forms triclinic crystals in space group P1̄ with a = 15.760 (5) Å, b = 14.848 (5) Å, c = 13.632 (4) Å, α = 70.4 (2)°, β = 118.5 (2)°, γ = 123.1 (2)°, V= 2336.6 (1) Å3, and Z = 2. The trinuclear cation resides on a general position but is very similar to the one in the acetate and has essentially D3h symmetry. The important dimensions within the [Mo3O2(O2CR)6(H2O)3]2+ ions are virtually identical in the two cases, with Mo-Mo = 2.766 (2) Å in the acetate and averaging 2.752 (3) Å in the propionate. This type of trinuclear cation can be formulated electronically as having six electrons for Mo-Mo bonding and bond orders of 1. They are very similar to the analogous [W3O2(02CR)6(H2O)3]2+ cations described earlier.
AB - The preparation and structural characterization of two trinuclear molybdenum(IV) cluster compounds with capping oxygen atoms are reported. Reaction of Mo(CO)6 with acetic acid under O2 allows the isolation, after suitable workup by cation-exchange resin chromatography of 1, [Mo3O2(OAc)6(H2O)3]Br2-H2O. This forms rhombohedral crystals in space group R3̄m with unit cell dimensions a = 11.784 (5) Å, a = 106.34 (5)°, V= 1386.6 (1) Å3, and Z = 2. The structure consists of [Mo3O2(O2CCH3)6(H2O)3]2+ ions having effectively D3h symmetry residing on crystallographic positions of C3v symmetry. The metal atoms form an equilateral triangle capped above and below by oxygen atoms. The edges of the triangle are each bridged by two acetate ions, and there is a water molecule coordinated to each metal atom with the Mo-OH2 bond direction intersecting the center of the opposite Mo-Mo bond. The bromide ions and the additional H2O are disordered over several positions in the rhombohedral cell. Reaction of Mo2(O2CCH3)4 with a mixture of propionic acid and propionic anhydride followed by cation column chromatography using CF3SO3H to elute gives [Mo3O2(O2C-C2H5)6(H2O)3](CF3SO3)2(CF3SO3H)(H2O)4. This forms triclinic crystals in space group P1̄ with a = 15.760 (5) Å, b = 14.848 (5) Å, c = 13.632 (4) Å, α = 70.4 (2)°, β = 118.5 (2)°, γ = 123.1 (2)°, V= 2336.6 (1) Å3, and Z = 2. The trinuclear cation resides on a general position but is very similar to the one in the acetate and has essentially D3h symmetry. The important dimensions within the [Mo3O2(O2CR)6(H2O)3]2+ ions are virtually identical in the two cases, with Mo-Mo = 2.766 (2) Å in the acetate and averaging 2.752 (3) Å in the propionate. This type of trinuclear cation can be formulated electronically as having six electrons for Mo-Mo bonding and bond orders of 1. They are very similar to the analogous [W3O2(02CR)6(H2O)3]2+ cations described earlier.
UR - http://www.scopus.com/inward/record.url?scp=0008266842&partnerID=8YFLogxK
U2 - 10.1021/ic00135a041
DO - 10.1021/ic00135a041
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:0008266842
SN - 0020-1669
VL - 21
SP - 1912
EP - 1917
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -