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

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journal contribution
posted on 12.12.2018, 14:04 by Arián E. Roa, Verónica Salazar, Daniel Mendoza-Espinosa, Margarita Paneque, Antonio Rodríguez-Diéguez, Ana M. Rodríguez, Juan Tejeda, José A. Castro-Osma, Antonio Otero, Agustín Lara-Sánchez
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(CH3CN)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)­{PdCl22-NN-bpzcp)}] (10), and [Ir­(η5-Cp-bpzcp)­(η2-CH2CH2)2(μ-bpzcp)­{PdCl22-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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