Binap as an 8e arene-mono-phosphine donor to Ru(II)

The reaction of the cationic hydride complex [RuH((eta)^6-benzene) (Binap)]CF3SO3 with PPh3 at 80 °C afforded complex 4 in excellent yield. The reaction with tri(p-tolyl) phosphine afforded an analogous compound, 5. After loss of the complexed benzene, the Ru-cation generated chooses to stabilize itself by coordinating the proximate naphthyl ring at the expense of one of the two phosphorus donors. The solid-state structure of 4 is reported and reveals that the (eta)^6 arene is strongly distorted towards a (eta)^4-mode.