Non-aromatic stabilised form of 3,4-difluoropyrrole at triosmium clusters: N–H and C–H versus C–F activation

Reaction of 3,4-difluoropyrrole with the labile triosmium cluster [Os3(CO)10(CH3CN)2] affords products in which C–H, N–H and C–F bonds are cleaved under mild conditions. C–H and N–H bonds are cleaved to give [Os3H(NCCFCFCH2)(CO)10] (1) a non-aromatic stabilised form of 3,4-difluoropyrrole. Thermolysis of 1 affords in moderate yields the compounds [Os3H2(CCCFCHNH)(CO)9] (2) and [Os3H2(NCHCFCFC)(CO)9] (3). For compound 3, C–H and N–H bonds are cleaved with concomitant migration of H atoms to the metal framework. In contrast, for compound 2 activation of C–H and C–F bonds leads to coordination of the ligand through the carbon atoms, acting as a four-electron donating species.

Graphical abstractTriosmium cluster activation leads to cleavage of a C–F bond in 3,4-difluoropyrrole with concomitant C–H bond cleavage and H migration to the metal framework, to give a trinuclear nonacarbonyl species showing a modified pyrrole ligand.Figure optionsDownload full-size imageDownload as PowerPoint slide