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
Journal of Organometallic Chemistry. Bd. 533. H. 1-2. Amsterdam: Elsevier 1997 S. 31 - 43
Erscheinungsjahr: 1997
ISBN/ISSN: 1872-8561
Publikationstyp: Zeitschriftenaufsatz
Sprache: Englisch
Doi/URN: 10.1016/S0022-328X(96)06824-6
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Inhaltszusammenfassung
The reaction of Fe-2(CO)(9) with heterocyclic imines derived from thiophene 2-carbaldehyde or N-methyl-pyrrole-2-carbaldehyde produces the dinuclear compounds [mu(2)-eta(3)-(R)N-CH2-C=C-C(H)-X(H)-X]Fe-2(CO)(6) (R=Ph, C6H11, p-Bu-t-C6H4; X=S, NMe). The analogous reaction with imines of thiophene-3-carbaldehyde or indole-3-carbaldehyde yields the corresponding isomeric clusters [mu(2)-eta(3)-(R)N-CH2-C=C-X-C(R')=C(R '')]Fe-2(CO)(6) (R=Ph, C6H11, R'=R ''=H, X=S: R=Ph, p-Bu-t-C6H4, R'=R ''=-C6H4-...The reaction of Fe-2(CO)(9) with heterocyclic imines derived from thiophene 2-carbaldehyde or N-methyl-pyrrole-2-carbaldehyde produces the dinuclear compounds [mu(2)-eta(3)-(R)N-CH2-C=C-C(H)-X(H)-X]Fe-2(CO)(6) (R=Ph, C6H11, p-Bu-t-C6H4; X=S, NMe). The analogous reaction with imines of thiophene-3-carbaldehyde or indole-3-carbaldehyde yields the corresponding isomeric clusters [mu(2)-eta(3)-(R)N-CH2-C=C-X-C(R')=C(R '')]Fe-2(CO)(6) (R=Ph, C6H11, R'=R ''=H, X=S: R=Ph, p-Bu-t-C6H4, R'=R ''=-C6H4-, X=NH). The reaction proceeds via activation of the C,H bond in beta-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 mu(2)-eta(3)-enyl-amido ligands being coordinated to an Fe-2(CO)(6) moiety, which is confirmed by X-ray structure analyses of six compounds. » weiterlesen» einklappen
