Journal of the American Chemical Society · 2014 · 140 citations · 29 references
Natural SciencesChemistryInorganic ChemistryOrganometallic ChemistrySupramolecular ChemistryChemical BondingCoordination ChemistryIntermolecular InteractionsMetal-ligand BondingTransition Metal ChemistryTransition Metal ComplexesActivation Of Small Molecules By Metal-ligand BondingFrustrated Lewis PairsIntermolecular Metal-ligand InteractionsLigand Effects On ReactivityMetal Ligand CoordinationReactivityRedox-active Small MoleculesSteric Accessibility
The synthesis of a three-coordinate Pt-borane complex featuring a bidentate "LZ" (boryl)iminomethane (BIM) ligand is reported. Unlike other LZ-type borane ligands featuring a single-donor buttress, the small bite angle enforced by the BIM ligand is shown to promote a significant metal-borane reverse-dative σ-interaction akin to multiply strapped metalloboratranes. The steric accessibility of the reactive Pt → B bond fostered by the BIM ligand allows for a rich reactivity profile toward small molecules that exploit metal-borane cooperative effects. The unligated (boryl)iminomethane BIM is also synthetically accessible and functions as a Frustrated Lewis Pair (FLP). The ability of the free BIM to effect bond activation reactions is contrasted with the behavior seen in the corresponding platinum-bound complexes.
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