SYNTHESES, STRUCTURES, AND PROPERTIES OF VANADIUM, COBALT, AND NICKEL COMPOUNDS WITH 2-MERCAPTOPHENOL

Three new compounds of 2-mercaptophenolate (mp2−), trinuclear (Et4N)[V3(mp)6] (1a) or (Ph4P)[V3(mp)6] (1b), dimeric (Et4N)2[Co(mp)(Hmp)]2 (2), and binuclear (Et4N)2[Ni2(mp)2(Hmp)2] (3), were synthesized and their structures determined. Compound 1b crystallizes in the triclinic space group P1 with a = 14.127 (4) Å, b = 14.342 (4) Å, c = 15.878 (4) Å, α = 65.08 (2)°, β = 73.09 (2)°, γ = 78.68 (2)°, V = 2781.3 Å3, and Z = 2. Compound 2 crystallizes in the monoclinic space group P21/c with a = 16.606 (2) Å, b = 15.575 (1) Å, c = 17.725 (2) Å, β = 111.07(1)°, V = 4277.8 Å3, and Z = 4. Compound 3 crystallizes in the monoclinic space group P21/n with a = 9.179 (4) Å, b = 17.487 (5) Å, c = 12.840 (4) Å, β = 92.87 (3)°, V = 2058.6 Å3, and Z = 2. Structural analyses revealed the multifunctional chelating character of mp2−: it can be StOt (t for terminal) as in 2, 3, and (Et4N)2[Fe2(mp)4]13 (4), StOb (b for bridging) as in 1b and 4, or SbOH as in 3. Some structural regularities are observed. Compounds 1b and 2 arc paramagnetic with magnetic moments of 2.76 and 2.38 μB per molecule in the polycrystalline state, respectively. Compound 2 dissociates in DMSO to its monomer, which is rapidly oxidized by trace air. The final product is purple [Co(mp)2]− with a magnetic moment of 3.26 μB. A simulated 1H NMR spectrum of 3 revealed the nuclear spin coupling of the hydrogen atom in the hydroxyl group with the ortho H on the same phenyl ring. © 1990, American Chemical Society. All rights reserved.