Reactivity of Terminal Iron Borylenes and Bis(borylenes) with Carbodiimides: Cycloaddition, Metathesis, Insertion and C−H Activation Pathways. Issue 45 (30th September 2021) - Matler, Alexander
Abstract: The reactions of carbodiimides with the iron arylborylene complex [Fe=BDur(CO)3 (PMe3 )] (Dur=2, 3, 5, 6‐Me4 C6 H) and the iron bis(borylene) complex [Fe{=BDur}{=BN(SiMe3 )2 }(CO)3 ] yield a wide variety of temperature‐dependent products, including known FeBNC and novel FeBNB metallacycles, complexes of N‐heterocyclic boracarbene and spiro‐boracarbene ligands and a unique 1, 3, 2, 4‐diazadiborolyl pianostool complex, characterized by NMR spectroscopy and X‐ray crystallography. The product distributions can be rationalized by considering sequences of cycloaddition, metathesis, insertion, and C−H activation pathways mainly governed by sterics. Abstract : The reactions of carbodiimides with iron borylene and bis(borylene) complexes yield a variety of products, including known FeBNC and novel FeBNB metallacycles, complexes of N‐heterocyclic boracarbene ligands, and a unique 1, 3, 2, 4‐diazadiborolyl pianostool complex. The product distributions can be rationalized by considering sequences of cycloaddition, metathesis, insertion, and C−H activation pathways mainly governed by sterics.