191922-43-7Relevant articles and documents
C,H bond activation of imino substituted heterocycles: Synthesis and crystal structure of [μ2-η3-( R) N-CH2-C=C-C(H) =C(H)-X ]Fe2( CO) 6 and the isomeric clusters [μ2-η3-(R)N-CH2-C=C-X-C(R′)=C(R″)]Fe2(CO)6
Imhof, Wolfgang
, p. 31 - 43 (2007/10/03)
The reaction of Fe2(CO)9 with heterocyclic imines derived from thiophene-2-carbaldehyde or N-methyl-pyrrole-2-carbaldehyde produces the dinuclear compounds [μ2-η3-(R)N-CH2-C=C-C(H)-X(H)-X]Fe2(CO)6 (R = Ph, C6H11, p-tBu-C6H4; X = S, NMe). The analogous reaction with imines of thiophene-3-carbaldehyde or indole-3-carbaldehyde yields the corresponding isomeric clusters [μ2-η3-(R)N-CH2-C=C-X-C(R′)=C(R″)Fe2(CO)6 (R = Ph, C6H11, R′ = R″ = H, X = S; R = Ph, p-tBu-C6H4, R′ = R″ = -C6H4-, X = NH). The reaction proceeds via activation of the C,H bond in β-position relative to the exocyclic C,N double bond of the imine ligands. A 1,3 hydrogen shift reaction then leads to the formation of a methylene group instead of the former imine carbon atom. So, the imine ligands are transformed into μ2-η3-enyl-amido ligands being coordinated to an Fe2(CO)6 moiety, which is confirmed by X-ray structure analyses of six compounds.
