Binap and MeO-Biphep complexes of Ru(II). Dicationic ligands as 6e donors. Unexpected cyclometallation in connection with P-C bond breaking

A series of cationic and dicationic Ru-arene complexes with Binap (1a) and MeO-Biphep (1b) have been prepared. C-13 NMR studies are shown to be useful in connection with recognising the 6e-bonding mode of 1a and 1b in the dications [Ru(1a or 1b)(eta (6)-arene)](SbF6)(2) (8,9). Reaction of 8,9 with: (a) (Bu4N)(Ph3SiF2) leads to a cyclometallated product which arises via P-C bond breaking and P-F bond making; (b) methanol provides a straightforward synthesis of the corresponding hydrides. C-13 NMR p-cymene chemical shifts are reported.