Abstract
New chiral ruthenium(II) allenylidene complexes were synthesized, and their reactivity with nucleophiles to give alkynyl complexes was investigated. The new allenylidene complex (RRu,Rax)-[Ru(Ind)(PPh3)(6){═C═C═C(t-Bu)(2-naphthyl)}]+PF6– was synthesized from the chloro precursor complex (RRu,Rax)-[RuCl(Ind)(PPh3)(6)] and the racemic propargylic alcohol HC≡CC(OH)(t-Bu)(2-naphthyl) and obtained in 96% yield, where (Rax)-6 is a chiral phosphoramidite and Ind an anionic indenyl ligand. The precursor and the allenylidene complex are chiral-at-metal, and the chiral information is completely transferred from the chloro precursor to the product allenylidene complex, both of which show the same absolute configuration, as demonstrated by X-ray diffraction. Together with the known allenylidene complex (RRu,Rax)-[Ru(Ind)(PPh3)(6)(═C═C═CPh2)]+PF6–, the attack of n-BuLi, MeLi, LiC≡CPh, and lithium 1-phenylethenolate nucleophiles on the allenylidene chain of (RRu,Rax)-[Ru(Ind)(PPh3)(6){═C═C═C(t-Bu)(2-naphthyl)}]+PF6– wa...
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