Bis(imino)pyridine ligand deprotonation promoted by a transient iron amide.
Addition of 2 equiv of LiNMe(2) to the bis(imino)pyridine ferrous dichloride, ((i)(Pr)PDI)FeCl(2) ((i)(Pr)PDI = (2,6-(i)()Pr(2)-C(6)H(3)N=CMe)(2)C(5)H(3)N), resulted in deprotonation of the chelate methyl groups, yielding the bis(enamide)pyridine iron dimethylamine adduct, ((i)(Pr)PDEA)Fe(NHMe(2)) ((i)(Pr)PDEA = (2,6-(i)Pr(2)-C(6)H(3)NC=CH(2))(2)C(5)H(3)N). Performing a similar procedure with KN(SiMe(3))(2) in THF solution afforded the corresponding bis(THF) adduct, ((i)(Pr)PDEA)Fe(THF)(2). ((i)(Pr)PDEA)Fe(NHMe(2)) has also been prepared by addition of the free amine to the iron dialkyl complex, ((i)(Pr)PDI)Fe(CH(2)SiMe(3))(2), implicating formation of a transient iron amide that is sufficiently basic to deprotonate the bis(imino)pyridine methyl groups. Deprotonation of the amine ligand in ((i)(Pr)PDEA)Fe(NHMe(2)) has been accomplished by addition of amide bases to afford the ferrous amide-ate complexes, [((i)(Pr)PDEA)Fe(mu-NMe(2))M] (M = Li, K).
Bouwkamp
Marco W
MW
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
Lobkovsky
Emil
E
Chirik
Paul J
PJ