Competing Magnetic Exchange Interactions in Tetranuclear d(1) Systems: Synthesis, Structure, and Magnetochemistry of a Neutral Vanadium(IV) Complex with a {(VO)(4)(&mgr;(3)-OR)(2)(&mgr;(2)-OR)(4)}(2+) Core.
The complex [{VO(L)}(2){VO(acac)}(2)(&mgr;(2)-OMe)(2)] 1 can be synthesized by reaction of the Schiff base ligand N,N-bis(2-hydroxyethyl)-N'-(2-pyrrolylmethylidene)ethylenediamine (H(2)L) with [VO(acac)(2)] (Hacac = 2,4-pentanedione). The compound 1.MeOH has been characterized by IR, UV/vis, and ESR spectroscopy as well as magnetic susceptibility measurements. A single-crystal diffraction study performed on 1. MeOH gives the following crystal data: triclinic, P&onemacr;, a = 7.352(2) Å, b = 12.584(4) Å, c = 12.826(4) Å, alpha = 107.61(2) degrees, beta = 102.96(2) degrees, gamma = 95.25(2) degrees, Z = 1. The tetranuclear {(VO)(4)(&mgr;(3)-OR)(2)(&mgr;(2)-OR)(4)}(2+) core of 1 is composed of three different types of edge-shared binuclear units, an anti-coplanar, two syn-coplanar, and two twist configurations. Consistent with this connectivity pattern, analysis of the magnetic data reveals competing ferromagnetic and antiferromagnetic exchange interactions within the tetranuclear core structure. Both ESR and magnetic data indicate a singlet ground state for 1. In addition, the general magnetic behavior of oxovanadium(IV) clusters is discussed on the basis of classification schemes derived from simple binuclear fragmentation patterns. Consistent with the superexchange mechanism expected to be operative for binuclear oxovanadium(IV) units with syn-coplanar configuration, the corresponding magnetic exchange parameter J(sc) of 1 (V.V = 3.410(2) Å) is determined to be antiferromagnetic at -153 cm(-)(1).
Plass
Winfried
W
Fakultät für Chemie, Lehrstuhl für Anorganische Chemie I, Universität Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany.