Ligand Effects in Carbon−Boron Coupling Processes Mediated by σ‐BH Platinum Complexes

The reaction of tri‐coordinated boranes (derived from dioxaborolanes and diazaborolanes) with cyclometalated low‐electron count platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC=ItBuiPr, IMes, IMes*) led, at low temperature, to the formation of the corresponding σ‐BH species. Some of these species have been characterized by X‐Ray diffraction methods showing a rare η1‐coordination mode. These compounds are thermally unstable and undergo a carbon‐boron coupling process whose reversibility depends on the NHC ligand. DFT calculations indicate that the energy barriers required for C−B bond formation events (together with Pt−H bonds) are lower than the competitive reactions leading to C−H bond formation (and Pt−B bonds). However, the C−B coupling products appear to be formed under kinetic control with ItBuiPr ligands, whereas the relative low energy barrier leading to C−H bond formation is sufficiently low to form the thermodynamically more stable platinum boryl complexes at rt. The latter energy barrier is, nevertheless, too high for the systems bearing IMes and IMes* ligands. Cyclometallated low‐electron count Pt(II) species stabilized by N‐heterocyclic carbene ligands (NHCs) react with tri‐coordinated boranes to form σ‐BH complexes, some of which exhibit a η1‐coordination mode. These compounds can undergo competitive C−B/C−H coupling processes that depending on the nature of the NHC can be reversible or not. The effects of the substituents on the borane have been also investigated.