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New CO-free iron boryl complexes, CpFe(PR3)2(Bpin), are described. The CpFe(PEt3)2(Bpin) derivative is uniquely capable of UV-free arene borylation at 70 °C via a dissociative pathway. Catalytic C–H borylation does not proceed using either monometallic or heterobimetallic schemes, and this failure is rationalized through analysis of relative pKa values for the corresponding iron hydride species.

Graphical abstract: Thermal C–H borylation using a CO-free iron boryl complex

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