Early metal di- and tricyanometalates: Useful building blocks for constructing magnetic clusters

Treatment of mer-VCl3(THF)3 with KTp [Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate], followed by [NEt4]CN in acetonitrile, affords [NEt4][(Tp)V(III)(CN)3].H2O (1.H2O); aerobic oxidation affords [NEt4][(Tp)V(IV)(O)(CN)2] (2). Subsequent treatment of 2 with Mn(II)(OTf)2 (OTf = trifluoromethanesulfonate) and 2,2'-bipyridine affords {[(Tp)V(O)(CN)2]2[Mn(II)(bipy)2]2[OTf]2}.2MeCN (3). Magnetic measurements indicate that 1-3 exhibit S = 1, (1/2), and 4 spin ground states, respectively.