The treatment of trans-[RuCl 2 (dppm) 2 ] with isocyanides in different reaction conditions affordstrans -[RuCl(CNR)(dppm) 2 ]Cl (3a: R = t Bu, 3b: R = Ph), trans-[RuCl(CNR)(dppm) 2 ]PF 6 (4a and 4b),trans -[RuCl(CNR) 2 (dppm)(dppm-P)]PF 6 (6a and 6b), andtrans -[Ru(CNR) 2 (dppm) 2 ](PF 6 ) 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 H 2 O 2 to givetrans -[RuCl(CNR) 2 (dppm)(dppmO-P)]PF 6 (8), which was transformed totrans -[Ru(CNR) 2 (dppm)(dppmO)](PF 6 ) 2 (9) by treatment with TIPF 6 .