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The Aza-Cope Rearrangement in Transition Metal Complexes. Construction of an Unsaturated C 7 -Ligand from Butadiyne and an Allylic Amine

1997; American Chemical Society; Volume: 16; Issue: 20 Linguagem: Inglês

10.1021/om9704511

ISSN

1520-6041

Autores

Rainer F. Winter, Fridmann M. Hornung,

Tópico(s)

Organometallic Complex Synthesis and Catalysis

Resumo

cis-RuCl2(L2)2 reacts with butadiyne in the presence of NaPF6 to give the butatrienylidene intermediate trans-[RuCl(L2)2CCCCH2]+, which can be trapped with tertiary amines to afford the ammoniobutenynyl complexes trans-[RuCl(L2)2C⋮CC(NR3) CH2]+ (L2 = dppm; R = Et, Pr). The respective N-allyl derivatives trans-[RuCl(L2)2C⋮CC((NMe2)allyl) CH2]+ (L = dppm, depe) rearrange under ambient conditions via an aza-Cope process to the amino-substituted allenylidene complexes trans-[RuCl(L2)2 CCC(NMe2)(CH2)2CHCH2]+.

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