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(P^EtN^MeP^Et)(CO)₃ (P^EtN^MeP^Et = (Et₂PCH₂)₂NMe) at Fe or N. Protonation of Fe(P^EtN^MeP^Et)(CO)₃ by [(Et₂O)₂H]⁺[B(C₆F₅)₄]⁻ occurs at the metal to give the iron hydride [Fe(P^EtN^MeP^Et)(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(P^EtN^MeP^Et)(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.