A Sulfur-Capped Triangular Cobalt–Tributylphosphine–Aminobenzenethiolato Complex: Synthesis, Structure and Properties of Co3(μ3-S)(abt)3(PBun3)3

Abstract

Abstract The reaction of CoCl2, Habt (2-aminobenzenethiol), NaOMe and PBun3 (tributylphosphine) in an equimolar ratio under anaerobic conditions, followed by the addition of an excess of Li2S led to the triangular cluster complex Co3(μ3-S)(abt)3(PBun3)3. It crystallizes in the triclinic space group , with a = 13.231(2), b = 14.201(2), c = 18.890(2) Å, α = 79.970(10)°, β = 87.560(10)°, γ = 67.040(1)°, V = 3216.6(12) Å3 and Z = 2. The molecule consists of three “Co(abt)(PBun3)” units with the Co3 plane capped by the bridging μ3-S atom to form an approximately equilateral triangle with an average Co–Co distance of 2.709 Å. The cobalt atoms located in distorted trigonal-bipyramidal environments are further bridged by μ2-S atoms from the three abt ligands and terminally coordinated by N and P donors. The cyclic voltammogram showed three quasi-reversible redox processes with E1/2 = 0.79, −0.07, and −0.81 V, vs. SCE. The variable-temperature magnetic susceptibility measurements showed an antiferromagnetic exchange interaction within the triangular spin cluster.