A study of the reactivity of trans-[RuCl2(dppm)2] toward isocyanides

Article abstract of DOI:10.1016/S0022-328X(96)06536-9

The treatment of trans-[RuCl₂(dppm)₂] with isocyanides in different reaction conditions affords trans-[RuCl(CNR)(dppm)₂]Cl (3a: R = ^tBu, 3b: R = Ph), trans-[RuCl(CNR)(dppm)₂]PF₆ (4a and 4b), trans-[RuCl(CNR)₂(dppm)(dpprn-P)]PF₆ (6a and 6b), and trans[Ru(CNR)₂(dppm)₂](PF₆)₂ (7a and 7b). During the course of these reactions several intermediates resulting from ring-opening and -closing processes of the dppm ligands were spectroscopically characterized. Finally, 6a was selectively oxidized with H₂O₂ to give trans-[RuCl(CNR)₂(dppm)(dppmO-P)]PF₆ (8), which was transformed to trans-[Ru(CNR)₂(dppm)(dppmO)](PF₆)₂ (9) by treatment with TIPF₆.