Reactions of [Mn(CO)3{η5-C5H4[( η5-C6H6)Mn(CO)3]}] and [WMe(CO)3{η5-C5H4[( η5-C6H6)Mn(CO)3]}] with aryllithium reagents

Abstract

The reactions of [Mn(CO) ₃ {η ⁵ -C ₅ H ₄ [( η ⁵ -C ₆ H ₆ )Mn(CO) ₃ ]}] 1 and [WMe(CO) ₃ {η ⁵ -C ₅ H ₄ [( η ⁵ -C ₆ H ₆ )Mn(CO) ₃ ]}] 2 with aryllithium reagents, LiR (R = o-, m-, p-MeC ₆ H ₄ , Ph, p-MeOC ₆ H ₄ or p-CF ₃ C ₆ H ₄ ), in diethyl ether at low temperature afforded acylmetalate intermediates, which on alkylation with Et ₃ OBF ₄ in aqueous solution at 0 °C gave alkoxycarbene complexes [Mn(CO) ₃ {η ⁵ -C ₅ H ₄ [( η ⁵ -C ₆ H ₆ )(OC) ₂ Mn C(OEt)R]}] and [WMe(CO) ₃ {η ⁵ -C ₅ H ₄ [( η ⁵ -C ₆ H ₆ )(OC) ₂ Mn C(OEt)R]}]. The structure of [Mn(CO) ₃ {η ⁵ -C ₅ H ₄ [( η ⁵ -C ₆ H ₆ )(OC) ₂ Mn C(OEt)C ₆ H ₄ Me-o]}], established by X-ray diffraction, shows that the carbene ligand is attached to the manganese atom co-ordinated to the η ⁵ -cyclohexadienyl moiety.