Anion control of tautomeric equilibria: Fe-H vs. N-H influenced by NH···F hydrogen bonding.

ABSTRACT: Counterions can play an active role in chemical reactivity, modulating reaction pathways, energetics and selectivity. We investigated the tautomeric equilibrium resulting from protonation of Fe(PEtNMePEt)(CO)3 (PEtNMePEt = (Et2PCH2)2NMe) at Fe or N. Protonation of Fe(PEtNMePEt)(CO)3 by [(Et2O)2H]+[B(C6F5)4]- occurs at the metal to give the iron hydride [Fe(PEtNMePEt)(CO)3H]+[B(C6F5)4]-. In contrast, treatment with HBF4·OEt2 gives protonation at the iron and at the pendant amine. Both the FeH and NH tautomers were characterized by single crystal X-ray diffraction. Addition of excess BF4 - to the equilibrium mixture leads to the NH tautomer being exclusively observed, due to NH···F hydrogen bonding. A quantum chemical analysis of the bonding properties of these systems provided a quantification of hydrogen bonding of the NH to BF4 - and to OTf-. Treatment of Fe(PEtNMePEt)(CO)3 with excess HOTf gives a dicationic complex where both the iron and nitrogen are protonated. Isomerization of the dicationic complex was studied by NOESY NMR spectroscopy.

SUBMITTER: Chambers GM 

PROVIDER: S-EPMC6369578 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature