1333210-72-2Relevant academic research and scientific papers
C-H activation via carbodiimide insertion into yttrium-carbon alkynide bonds: An organometallic Alder-ene reaction
Casely, Ian J.,Ziller, Joseph W.,Evans, William J.
, p. 4873 - 4881 (2011)
The yttrium alkynide (C5Me5)2Y(C≡ CPh)(THF), 1, and the related trienediyl [(C5Me5) 2Y2(μ-η2:η2-PhC=C=C=CPh), 2, can be isolated from the reaction of (C5Me5) 2Y(η3-CH2CHCH2)(THF) with phenylacetylene in THF and hexane, respectively. Complex 1 reacts with tBuN=C=NtBu to afford the conventional amidinate insertion product (C5Me5)2Y[tBuNC(C≡ CPh)NtBu-κ2N,N′, 3. However, the analogous reaction with iso-propyl and cyclohexyl carbodiimides involves C-H activation and forms the iminovinyl complexes (C5Me5) 2Y[C(=CHPh)C(N=CMe2)=NiPr-κ2C, N, 4, and (C5Me5)2Y{C(=CHPh)C[N=C(CH 2)5=NCH(CH2)5-κ2C, N}, 5, respectively. The reaction is formally a variation of the Alder-ene reaction in which a C-H bond of the carbodiimide (ene) is activated and transferred to the alkynide ligand (enophile) bound to yttrium. The trienediyl 2 reacts with iso-propyl carbodiimide via conventional insertion to form a bis(amidinate) product with a trienediyl linker, namely, (C5Me 5)2Y[μ-κ2-(iPrN) 2C-C(Ph)=C=C=C(Ph)-C(NiPr)2Y(C 5Me5)2, 6. The alkynide ligand in 1 is also modified in the reaction with benzylcyanide that forms an unusual insertion product, the amidonitrile complex [(C5Me5) 2Y{μ-N(H)C(CH2Ph)=C[C(Ph)=CHPhC≡N}2, 7.
