Transition-metal dithiolene complexes. Part XVII. Cleavage of the ring from π-cyclopentadienyl–metal complexes by 1,2-dithiolato- and dithiocarbamato-ligands
Abstract
The displacement of π-C5H5 rings from [(π-C5H5)2TiCl2], [(π-C5H5)Mo(NO)I2]2, [(π-C5H5)Mn(NO)(CO)2]-[PF6], [(π-C5H5)Fe(NO)]2, and [π-C5H5Ni(CO)]2, by the dithiolato-ligands {S2C2(CN)2}2–, {S2C6Cl4}2– or {S2C6H3Me}2–, and by {S2C·NMe2}–, is discussed. Reaction of [(π-C5H5)2TiCl2] with one, two, or three moles of {S2C6Cl4}2– gave [(π-C5H5)2TiS2C6Cl4], [(π-C5H5)Ti(S2C6Cl4)2]– and [Ti(S2C6Cl4)3]2–, respectively. Treatment of [(π-C5H5)Mn(NO)(CO)2][PF6] with K2S2C6Cl4, in the presence of potassium chloride in ethanol, afforded [Mn(NO)(S2C6Cl4)2]2–, and evidence for [Mn(NO)(S2C6H3Me)2]2– and [Mn(NO){S2C2(CN)2}{S2C6Cl4}]2– is presented; [Mn(NO){S2C2(CN)2}2]2– was obtained by treating manganese(II) chloride with nitric oxide and {S2C2(CN)2}2– or by reaction of [Mn{S2C2(CN)2}2]2– with nitric oxide. The NO stretching frequencies of these new manganese nitrosyl dithiolenes are briefly discussed.
The known compounds [Fe(NO){S2C2(C·N)2}2]2– and [Fe(NO)(S2C·NMe2)2] were prepared by reaction of [(π-C5H5)Fe(NO)]2 with Na2S2C2(CN)2 and NaS2C·NMe2, respectively, and [Ni{S2C2(CN)2}2]2– was obtained directly from [(π-C5H5)Ni(CO)]2 and {S2C2(CN)2}2–.
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