No abstract

We report a novel iron(II) complex supported by an anionic phosphanyl-iminopyridinate ligand, Cp*Fe(Cy2PNC5H4N) (1), which shows remarkable catalytic activity in the selective hydroboration of CO2 with HBpin, producing boryl formate with a turnover frequency (TOF) of ∼1176 h–1 at room temperature. This catalysis involves cooperative metal–ligand reactivity for H–B bond activation, affording a key Fe(II)–H intermediate, Cp*FeH(Cy2PN(Bpin)C5H4N) (2), that binds the Bpin moiety at the non-coordinated amino site. The very fast and selective formoxy production can be conveniently coupled to the N-formylation of amines, which delivers a variety of formamides. In addition, the reduction of boryl formate to the CH3OBpin stage was also achieved by 1 with HBpin under N2.

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Inspired by OxdA that operates biocatalytic aldoxime dehydration, we have developed an efficient iron catalyst, Cp*Fe­(1,2-Cy2PC6H4O) (1), which rapidly converts various aliphatic and aromatic aldoximes to nitriles with release of H2O at room temperature. The catalysis involves redox activation of the N–O bond by a 1e– transfer from the iron catalyst to the oxime. Such redox-mediated N–O cleavage was demonstrated by the isolation of a ferrous iminato intermediate from the reaction of the ketoxime substrate. This iron-catalyzed acceptorless dehydration approach represents a general method for the preparation of nitriles, and it also delivers salicylonitriles by catalyzing the Kemp elimination reaction.