Exchange Coupling in Binuclear Manganese and Cobalt Complexes with the Tetraimido Sulfate Anion [S(NtBu)4]2.

The (hetero)bimetallic complexes [Cl2Mn(NtBu)2S(tBuN)2Mn{ClLi(THF)3}2] (1), [(acac)Co(NtBu)2S(tBuN)2Co(acac)] (2), and [(acac)Co(NtBu)2S(tBuN)2Li(THF)2] (3), with THF = tetrahydrofuran and acac = acetylacetonate [H2C(C(O)Me)2], were synthesized and investigated for their magnetic properties. While the two different MnII sites in 1 gave a weak coupling of J = -1.00 cm-1, we could observe an appreciable antiferromagnetic coupling of J = -6.08 cm-1 between the two CoII cations in 2, proving the tetraimido sulfate anion to be a challenging but promising linker to enhance magnetic communication between paramagnetic centers. The heterobimetallic complex 3 seems a versatile platform for magnetically interesting d/d, f/d, or f/f mixed-metal complexes.