Abstract
The ultrastrong and short intramolecular NHFe hydrogen bond in diferrocenyl hydrazone raises the barrier for intramolecular electron transfer in its mixed-valent cation and is only disrupted by double oxidation to .
Highlights
The ultrastrong and short intramolecular NHÁ Á ÁFe hydrogen bond in diferrocenyl hydrazone 2 raises the barrier for intramolecular electron transfer in its mixed-valent cation 2+ and is only disrupted by double oxidation to 22+
The redoxactive diferrocenyl tosylhydrazone 2 had been previously employed for the in situ generation of the highly reactive and elusive diferrocenyl carbene.[2]
DFT calculations suggest that the conformer with an intramolecular NHÁ Á ÁFe hydrogen bond (FeÁ Á ÁN distance 3.55 Å; FeÁ Á ÁH distance 2.67 Å) is more stable by 10 kJ molÀ1 with respect to a non-hydrogen bonded conformer
Summary
The ultrastrong and short intramolecular NHÁ Á ÁFe hydrogen bond in diferrocenyl hydrazone 2 raises the barrier for intramolecular electron transfer in its mixed-valent cation 2+ and is only disrupted by double oxidation to 22+. The absorption band for the NH stretching vibration of 2 is found at 3101 cmÀ1 in the solid state, significantly lower than that of the analogous diphenyl tosylhydrazone 3 (3219 cmÀ1; with intermolecular NHÁ Á ÁOS hydrogen bonds in the solid state;[5] ESI†). DFT calculations suggest that the conformer with an intramolecular NHÁ Á ÁFe hydrogen bond (FeÁ Á ÁN distance 3.55 Å; FeÁ Á ÁH distance 2.67 Å) is more stable by 10 kJ molÀ1 with respect to a non-hydrogen bonded conformer.
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