TY - JOUR
T1 - The Tetrakis(hydrogen phosphato)diniolybdenum Ion [Mo2(HPO4)4]2-. Compounds with a Metal-Metal Triple Bond Which Are Easily Prepared and Permanently Stable in Air
AU - Bino, Avi
AU - Cotton, F. Albert
PY - 1979
Y1 - 1979
N2 - The octachlorodimolybdate(II) ion, [Mo2Clg4-, reacts with 2 M orthophosphoric acid in air to form the purple [Mo2(HPO4)4]2-ion which can easily be isolated in combination with various cations, for example, as Cs2[Mo2(HPO4)4(H2Q)2], 1, and (C5NH6)3[Mo2(HPO4)4]Cl, 2, both of which have been fully characterized structurally. They are stable indefinitely in ordinary air at 25 °C. The [Mo2(HP04)4]22- ion has a paddlewheel structure very similar to that of the [Mo2(SO4)4]4-3 ions; the manner in which the rings are bent and the placement of the hydrogen atoms are such as to make the idealized symmetry C4h. The Mo-Mo triple bond lengths are 2.223 (2) and 2.232 (1) υ in 1 and 2, respectively. In each case there are axial ligands, but these are loosely bonded with Mo-OH2 distances of 2.46 (1) and 2.53 (1) υ in 1 and Mo-Cl distances of 2.910 (1) υ in 2. In 1 there is no crystallographically imposed symmetry, but the conformation is only 1.35° from being precisely eclipsed, while in 2 there is 2 /m crystallographic symmetry and the conformation is perfectly eclipsed. Compound 1 crystallizes in space group P21c with a=8.751 (3) υ, b=11.217 (3) υ, c=17.938 υ, β=90.92 (2)°, V=1761 (1) υ3, and Z=4. Compound 2 crystallizes in space group Pbam with a=18.329 (3) υ, b=9.157 (2) A, c=8.053 (1) A, V=1351 (1) υ3, and Z=2.
AB - The octachlorodimolybdate(II) ion, [Mo2Clg4-, reacts with 2 M orthophosphoric acid in air to form the purple [Mo2(HPO4)4]2-ion which can easily be isolated in combination with various cations, for example, as Cs2[Mo2(HPO4)4(H2Q)2], 1, and (C5NH6)3[Mo2(HPO4)4]Cl, 2, both of which have been fully characterized structurally. They are stable indefinitely in ordinary air at 25 °C. The [Mo2(HP04)4]22- ion has a paddlewheel structure very similar to that of the [Mo2(SO4)4]4-3 ions; the manner in which the rings are bent and the placement of the hydrogen atoms are such as to make the idealized symmetry C4h. The Mo-Mo triple bond lengths are 2.223 (2) and 2.232 (1) υ in 1 and 2, respectively. In each case there are axial ligands, but these are loosely bonded with Mo-OH2 distances of 2.46 (1) and 2.53 (1) υ in 1 and Mo-Cl distances of 2.910 (1) υ in 2. In 1 there is no crystallographically imposed symmetry, but the conformation is only 1.35° from being precisely eclipsed, while in 2 there is 2 /m crystallographic symmetry and the conformation is perfectly eclipsed. Compound 1 crystallizes in space group P21c with a=8.751 (3) υ, b=11.217 (3) υ, c=17.938 υ, β=90.92 (2)°, V=1761 (1) υ3, and Z=4. Compound 2 crystallizes in space group Pbam with a=18.329 (3) υ, b=9.157 (2) A, c=8.053 (1) A, V=1351 (1) υ3, and Z=2.
UR - http://www.scopus.com/inward/record.url?scp=0001336319&partnerID=8YFLogxK
U2 - 10.1021/ic50202a053
DO - 10.1021/ic50202a053
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AN - SCOPUS:0001336319
SN - 0020-1669
VL - 18
SP - 3562
EP - 3565
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 12
ER -