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Synthesis and Reactivity of IrIII Complexes Bearing C-Metalated Pyrazolato Ligands

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A bidentate triazolinylidene-pyrazole chelate ligand was metalated with [IrCp*Cl2]2 to give C,N-chelate complex [4]I. The N1-metalated pyrazole subsequently underwent a rollover metalation to give the complex with C5,C4-metalated pyrazolato ligand… Click to show full abstract

A bidentate triazolinylidene-pyrazole chelate ligand was metalated with [IrCp*Cl2]2 to give C,N-chelate complex [4]I. The N1-metalated pyrazole subsequently underwent a rollover metalation to give the complex with C5,C4-metalated pyrazolato ligand [5]. The reactivity of [5] toward insertion and protonation was investigated. Complex [5] was found to react with CO to give IrIII carbonyl complex [6]I, which subsequently reacted under migratory CO insertion into the Ir–C(pyrazolato) bond to give [7]. The reaction of [5] with the terminal alkyne methyl propiolate yielded 1,2 insertion product [8], featuring a 7-membered C,C-chelate ring.

Keywords: reactivity iriii; synthesis reactivity; metalated pyrazolato; reactivity; iriii complexes

Journal Title: Organometallics
Year Published: 2019

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