Well-defined iron bis(diphosphine) complexes are active catalysts for the dehydrogenative C-H borylation of aromatic and heteroaromatic derivatives with pinacolborane. The corresponding borylated compounds were isolated in moderate to good yields (25-73%) with a 5 mol% catalyst loading under UV irradiation (350 nm) at room temperature. Stoichiometric reactivity studies and isolation of an original trans-hydrido(boryl)iron complex, Fe(H)(Bpin)(dmpe)2, allowed us to propose a mechanism showing the role of some key catalytic species.
A new and efficient method based on the simple metalating reagent Fe(CO)5 has been developed for the straightforward synthesis of well defined cyclometalled PCP iron carbonyl pincer complexes. The reaction proceeds cleanly under mild conditions at 30 °C and UV irradiation. Four hydride pincer complexes are synthesized and fully characterized as well as an intermediate dinuclear species. The new iron complexes are active and selective catalytic precursors for the dehydrogenative borylation of styrene with HBpin.
Iron-Catalyzed C-H Borylation of Arenes. -Both aromatic and heteroaromatic arenes undergo dehydrogenative borylation with pinacolborane catalyzed by well--defined iron bis(diphosphine) complexes under UV irradiation. A possible mechanism is proposed based on an isolated hydrido(boryl)iron complex synthesized from pinacolborane and stoichiometric amount catalyst. -(DOMBRAY, T.; WERNCKE, C. G.; JIANG, S.; GRELLIER, M.; VENDIER, L.; BONTEMPS, S.; SORTAIS, J.-B.; SABO-ETIENNE, S.; DARCEL*, C.; J. Am. Chem. Soc. 137 (2015) 12, 4062-4065, http://dx.doi.org/10.1021/jacs.5b00895 ; Inst. Sci. Chim., CNRS, Univ. Rennes, F-35042 Rennes, Fr.; Eng.) -L. Grundl 35-215
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