TRANSITION METAL DITHIOLENE COMPLEXES .9. MANGANESE PI-CYCLOPENTADIENYL(NITROSYL)DITHIOLENE AND RELATED METAL COMPLEXES

The preparation of new monodithiolene complexes π-C5H4RMn(NO)(S-S)z, where R = H or CH3 and z = 0 or -1 and where S-S represents S2C2(CN)2, S2C6H3CH3, or S2C6Cl4, is reported. The analogous dithiocarbamates, π-C5H4RMn(NO)S2- CNR′02, where R′ = CH3 or C2H5, and 1,1-dicyanoethylene-2,2-dithiolenes, π-C6H4RMn(NO)S2C═C(CN)-2, are also described. These complexes have been investigated by voltammetry and it is shown that the 1,2-dithiolenes exist as part of a three-membered electron-transfer series, z = +1, 0, or -1, the 1,1-dithiolene is part of at least a two-membered series, z = 0 or -1, and the dithiocarbamates can be oxidized to monocations; the complexes have been further characterized by ir and esr spectroscopy. The voltammetric properties of certain x-cyclopentadienyldicyano-1,2-dithiolenes, (π-C5H5)2Ti-S2C2(CN)2, π-C5H5MS4C4(CN)-4 (M = Mo, W, or Ti), and π-C5H5CoS2C2(CN)2 are reported, and evidence for π-C2H3CoS2C2(CN)-2 is presented. © 1969, American Chemical Society. All rights reserved.