TY - JOUR
T1 - Syntheses, X-ray structural characterizations, and thermal stabilities of two nonclassical trinuclear vanadium(IV) complexes
AU - Maass, John S.
AU - Chen, Zhichao
AU - Zeller, Matthias
AU - Tuna, Floriana
AU - Winpenny, Richard E P
AU - Luck, Rudy L.
PY - 2012/3/5
Y1 - 2012/3/5
N2 - The preparation and structural characterization of two trinuclear vanadium complexes, (V 3(μ 3-O)O 2)(μ 2- O 2P(CH 2C 6H 5) 2) 6(H 2O), 1, and (V 3(μ 3-O)O 2)(μ 2-O 2P(CH 2C 6H 5) 2) 6(py), 2, are reported. In these nonclassical structures, the planar central core consists of the three vanadium atoms arranged in the form of an acute quasi-isosceles triangle with the central oxygen atom multiply bonded to the vanadium atom at the center of the vertex angle and weakly interacting with the two other vanadium atoms on the base sites, each of which contain one external multiply bonded oxygen atom. Reacting VO(acac) 2in the presence of diphenylphosphinic acid affords (VO(O 2PPh 2) 2) ∞, 3, while 2-hydroxyisophosphindoline-2-oxide at room temperature in CH 2Cl 2 affords ((H 2O)VO(O 2Po-(CH 2) 2C 6H 4) 2) ∞, 4, and at 120 °C in EtOH yields (VO(O 2P(o-(CH 2) 2(C 6H 4)) ∞, 5 on the basis of elemental analyses. The thermal and chemical stability of the complexes were assessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. The bond strengths of the vanadium atoms to the OH 2 ligand in 1 and to the NC 5H 5 ligand in 2 were assessed at 10.7 and 42.0 kJ/mol respectively. Room temperature magnetic susceptibility measurements reveal magnetic moments for trinuclear 1 and 2 at 3.02(1) and 3.05(1) μ B/mol, and also close to spin only values (1.73 μ B) values for 3, 4, and 5 at 1.77(2), 1.758(7), and 1.77(3) μ B, respectively. Variable-temperature, solid-state magnetic susceptibility measurements were conducted on complex 2 in the temperature range of 2.0-298 K and at an applied field of 0.5 T. Magnetization measurements at 2 and 4 K confirmed a very weak magnetic interaction between the vanadyl centers. © 2012 American Chemical Society.
AB - The preparation and structural characterization of two trinuclear vanadium complexes, (V 3(μ 3-O)O 2)(μ 2- O 2P(CH 2C 6H 5) 2) 6(H 2O), 1, and (V 3(μ 3-O)O 2)(μ 2-O 2P(CH 2C 6H 5) 2) 6(py), 2, are reported. In these nonclassical structures, the planar central core consists of the three vanadium atoms arranged in the form of an acute quasi-isosceles triangle with the central oxygen atom multiply bonded to the vanadium atom at the center of the vertex angle and weakly interacting with the two other vanadium atoms on the base sites, each of which contain one external multiply bonded oxygen atom. Reacting VO(acac) 2in the presence of diphenylphosphinic acid affords (VO(O 2PPh 2) 2) ∞, 3, while 2-hydroxyisophosphindoline-2-oxide at room temperature in CH 2Cl 2 affords ((H 2O)VO(O 2Po-(CH 2) 2C 6H 4) 2) ∞, 4, and at 120 °C in EtOH yields (VO(O 2P(o-(CH 2) 2(C 6H 4)) ∞, 5 on the basis of elemental analyses. The thermal and chemical stability of the complexes were assessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) measurements. The bond strengths of the vanadium atoms to the OH 2 ligand in 1 and to the NC 5H 5 ligand in 2 were assessed at 10.7 and 42.0 kJ/mol respectively. Room temperature magnetic susceptibility measurements reveal magnetic moments for trinuclear 1 and 2 at 3.02(1) and 3.05(1) μ B/mol, and also close to spin only values (1.73 μ B) values for 3, 4, and 5 at 1.77(2), 1.758(7), and 1.77(3) μ B, respectively. Variable-temperature, solid-state magnetic susceptibility measurements were conducted on complex 2 in the temperature range of 2.0-298 K and at an applied field of 0.5 T. Magnetization measurements at 2 and 4 K confirmed a very weak magnetic interaction between the vanadyl centers. © 2012 American Chemical Society.
U2 - 10.1021/ic201259u
DO - 10.1021/ic201259u
M3 - Article
SN - 0020-1669
VL - 51
SP - 2766
EP - 2776
JO - Inorganic Chemistry: including bioinorganic chemistry
JF - Inorganic Chemistry: including bioinorganic chemistry
IS - 5
ER -