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

摘要

A series of cationic and dicationic Ru-arene complexes with Binap (1a) and MeO-Biphep (1b) have been prepared. ~(13)C NMR studies are shown to be useful in connection with recognizing the 6e-bonding mode of 1a and 1b in the dications (Ru(1a or 1b)(#eta#~6-arene))(SbF_6)_2 (8,9). Reaction of 8,9 with: (a) (Bu_4N)(Ph_3SiF_2) leads to a cyclometallated product which arises via P-C bond breaking and P-F bond making; (b) methanol provides a straight-forward synthesis of the corresponding hydrides. ~(13)C NMR p-cymene chemical shifts are reported.