Insertion of CS2 and CSe2 into metal—amido bonds. Mono- versus bi-dentate dithiocarbamates formed by reactions of CS2 + NHR2 with {CpMo(CO)n}2 (M Fe, n 2; m Mo, n 3) |
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| Authors: | Enrique Román Daniel Catheline Didier Astruc |
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| Institution: | Laboratoire de Chimie des Organométalliques, ERA No. 477, Université de Rennes, 35042 Rennes Cédex France |
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| Abstract: | The reaction of Cp2Fe2(CO)4 with NHEt2 and CS2 gives the monodentate dithiocarbamate CpFe(CO)2-η1-SC(S)NEt2 (Ia), whereas the same reaction with CP2Mo2(CO)6 gives the chelate CPMo(CO)2-η2-S2CNEt2 (II). New complexes of amines CpFe(CO)2(NHR2)+PF6- (III, R Me, Et, SiMe3) have been synthesized by treating CpFe(CO)2Cl with NHR2. They do not react with CS2 and give only CpFe(CO)2]2 upon refluxing with bases such as t-BuOK or NEt(i-Pr)2, but concerted CS2 insertion in the presence of a base immediately gives I at 20°C. This clean route is used to synthesize the monodentate diselenocarbamate CpFe(CO)2-η1-SeC(Se)NMe2 (IV) by reaction of CSe2 with III (R Me) in the presence of t-BuOK. Whereas the known reaction of CpFe(CO)2Cl with Na+S2CNMe2? gives Ib (R Me), the analogous reaction of C5Me5Me(CO)2Br gives specifically the thermally stable chelate C5Me5Fe(CO)-η2-S2CNMe2 (Vb′). |
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