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Study of the Coordination Modes of Hybrid NNCp Cyclopentadienyl/Scorpionate Ligands in Ir Compounds.

Inorganic Chemistry 2018 December 13
A new coordination mode for the hybrid scorpionate/cyclopentadienyl ligand bpzcp, [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] is observed in iridium complexes. The reaction of the lithium precursor, [Li(bpzcp)(THF)], with a range of [IrCl(diene)]2 compounds leads to an unprecedented binding mode of the hybrid scorpionate/cyclopentadienyl ligand as η5 -Cp-coordinated and the formation of Ir(I) derivatives [Ir(η5 -Cp-bpzcp)(η4 -cod)] (1), [Ir(η5 -Cp-bpzcp){η4 -CH2 ═C(Me)C(Me)═CH2 }] (2), [Ir(η5 -Cp-bpzcp)(η2 -coe)2 ] (3), and [Ir(η5 -Cp-bpzcp)(η2 -CH2 ═CH2 )2 ] (4). The Ir(I) complex 4 reacts with CO or bromine to afford the compound [Ir(η5 -Cp-bpzcp)(CO)2 ] (5) and the 18e- Ir(III) complex [Ir(κ-N-η5 -Cp-bpzcpBr2 )Br2 ] (6), respectively. Reaction of the iridium compounds (2-4) with CuI or [PdCl2 (CH3 CN)2 ] yields the heterobimetallic iridium-copper or iridium-palladium complexes [Ir(η5 -Cp-bpzcp){η4 -CH2 ═C(Me)C(Me)═CH2 }(μ-bpzcp){CuI(κ2 -NN-bpzcp)}] (7), [Ir(η5 -Cp-bpzcp)(η2 -coe)2 }(μ-bpzcp){CuI(κ2 -NN-bpzcp)}] (8), [Ir(η5 -Cp-bpzcp)(η2 -CH2 ═CH2 )2 }(μ-bpzcp){CuI(κ2 -NN-bpzcp)}] (9), [Ir(η5 -Cp-bpzcp)(coe)2 }(μ-bpzcp){PdCl2 (κ2 -NN-bpzcp)}] (10), and [Ir(η5 -Cp-bpzcp)(η2 -CH2 ═CH2 )2 (μ-bpzcp){PdCl2 (κ2 -NN-bpzcp)}] (11). All products were characterized by spectroscopic methods and the X-ray crystal structures of 1, 2, 3, 4, and 6 were also established.

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