Iron(II) Mediated Deazotation of Benzyl Azide: Trapping and Subsequent Transformations of the Benzaldimine Fragment.

Abstract

The mono-benzaldimine (HN═CHPh) complex [(tBupyrpyrr2)Fe(HN═CHPh)] (1-HN═CHPh) has been prepared by reaction of [(tBupyrpyrr2)Fe(OEt2)] (1-OEt2) (tBupyrpyrr2 = 2,6-bis(3,5-di-tert-butyl-pyrrolyl)pyridine) with one equivalent of benzyl azide. Compound 1-HN═CHPh retains the cis-divacant octahedral coordination geometry akin to 1, as established by single crystal X-ray diffraction study. A bis-HN═CHPh complex [(tBupyrpyrr2)Fe(HN═CHPh)2] (2) was also prepared by the addition of two equivalents of benzyl azide to 1, and its molecular structure exhibits the two HN═CHPh ligands coordinated trans to each other, thereby forming a square pyramidal coordination geometry at the FeII center. Reaction of 1 with excess benzyl azide yields [(tBupyrpyrr2)Fe(HN═CHPh)2·PhCHNCH(NH2)Ph] (2-PhCHNCH(NH2)Ph), which contains an unstable benzylideneamino phenyl methanamine fragment, effectively hydrogen bonded to 2. Thermolysis of 2 or 2-PhCHNCH(NH2)Ph releases the HN═CHPh self-coupling products hydrobenzamide (A), N-benzylidine benzylamine (B), and benzonitrile (C). Under catalytic conditions, free HN═CHPh (cis/trans-HN═CHPh mixture) is produced using 2.5 mol % of 1 in 90% spectroscopic yield. These studies provide a clearer understanding for the conversion of the HN═CHPh in 2 or 2-PhCHNCH(NH2)Ph to the C-C and C-N coupled products. Reduction of 1-HN═CHPh with KC8 yields the reductively coupled benzylamide complex [K(OEt2)]2[(tBupyrpyrr2)2Fe2(μ2-NHCHPhCHPhNH)] (3) as the result of a new C-C bond formed between two radical benzylamide fragments.