Transition-metal dithiolene complexes. Part XVI. π-Cyclopentadienyl manganese nitrosyl 1,1-dithiolene complexes
Abstract
The syntheses of the 1,1-dithiolene complexes, [(π-C5H5)Mn(NO)S2C:X]–, [X = C(CN)·CO2Et, C(CN)·CO·NH2 and N·CN], and of [(π-C5H5)Mn(NO)S2C·NR2](R = Me or Et) are described. Both series of complexes undergo one-electron oxidation reactions which were detected voltammetrically, and the half-wave potentials were dependent on the nature of the sulphur ligand substituents. The NO stretching frequencies of the compounds were also dependent on the sulphur ligand substituents and on the overall charge on the complex. The existence of [(π-C5H5)Mn(NO)S2C·X]0 and of [(π-C5H5)Mn(NO)S2C·NR2]+ was confirmed by e.s.r. spectral studies and the g-tensors and ΔaMn‡ were significantly different from those obtained from the 1,2-dithiolene analogues, [(π-C5H5)Mn(NO)S2C2R2]0 and [Mn(π-C5H5)(NO)S2C6Cl4]0.