Formation of Iridabenzenes by Coupling of Iridacyclopentadienes and Alkenes

Álvarez, Eleuterio; Paneque, Margarita; Poveda, Manuel L.; Rendón, Nuria

doi:10.1002/anie.200502437

Cited by 82 publications

(27 citation statements)

References 29 publications

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“…In other words, the electronic structure of 6 may be thought of as being intermediate between those of I and II below, with a larger contribution of the former. This assumption was reinforced by the solid-state structural data obtained by X-ray crystallography [2] ( Figure 2 and Table 2). Even though the two Ir-C bond lengths are similar, the Ir-C(Et) bond [1.922(4) Å] is shorter than the Ir-C(CO 2 Me) bond [1.979(4) Å].…”

Section: Reaction Of Complex 1 With Propenementioning

confidence: 80%

“…4 )] [1; Tp Me2 = hydrotris(3,5-dimethylpyrazolyl)borate, R = CO 2 Me] with ethylene (Scheme 1). [1] The first species formed is the iridacycloheptadiene 2 as the result of the insertion of C 2 H 4 into one of the two identical Ir-C bonds.…”

Section: (R)=c(r)c(r)=c 4 (R)}(h 2 O)-(ir-cmentioning

confidence: 99%

“…Part of the findings reported herein have been briefly communicated. [2] [a] Instituto de Investigaciones Químicas and Departamento de Química Inorgánica, Consejo Superior de Investigaciones Científicas (CSIC) and Universidad de Sevilla, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain E-mail: paneque@iiq.csic.es nation from the resulting alkyliridium moiety.…”

Section: -(R)=c(h)c(r)=cunclassified

“…Different results are observed when compound 1 is treated with propene in CH 2 Cl 2 at 60°C; this reaction gives the mixture of compounds 6-8 shown in Equation (2). Complexes 6 and 7 were isolated as green and dark-yellow microcrystalline solids, respectively, by column chromatography on silica gel, although characterisation of 8 required its direct preparation from 7 (see below).…”

Section: Reaction Of Complex 1 With Propenementioning

confidence: 99%

“…The analytical and spectroscopic data for 6-8 support its proposed formulation, which for 6 was confirmed by an X-ray structure determination. (2) Compound 6, which is the major product of Equation (2), has an iridabenzene structure. Its formation from 1 and propene, that is, by coupling of an alkene with a metallacyclopentadiene, constitutes a novel synthetic procedure for this kind of aromatic metallacycle.…”

Section: Reaction Of Complex 1 With Propenementioning

confidence: 99%

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The Synthesis of Iridabenzenes by the Coupling of Iridacyclopentadienes and Olefins

et al. 2007

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The iridacyclopentadiene [(TpMe2)Ir{C1(R)=C(R)C(R)=C4(R)}(H2O)(Ir–C4)] (1; R = CO2Me) reacts with propene at 60 °C to give the iridabenzene [(TpMe2)Ir{C1(Et)C(R)C(R)C(R)C5(R)}(H)(Ir–C5)] (6), which also contains a hydride ligand, as the main product, accompanied by complexes 7 and 8 derived from the insertion of propene into the Ir–C bonds of 1. In contrast, the closely related metallacycle [(TpMe2)Ir{C1(R)=C(H)C(R)=C4(R)}(H2O)(Ir–C4)] (1‐H) gives the iridabenzene [(TpMe2)Ir{C1(Me)C(R)C(H)C(R)C5(R)}(Me)(Ir–C5)] (13), which contains an iridium‐bonded methyl group, upon treatment with propene at 20 °C. The proposed mechanism for the formation of metallabenzenes 6 and 13 postulates Ir–propene → Ir=CHEt or Ir–propene → Ir=CMe2 isomerisations, followed by insertion of the alkylidene ligand into an Ir–C(R) bond (regioselective for 1‐H) and α‐H or α‐Me elimination from the resulting alkyliridium moiety. At 25 °C, neat acetonitrile induces stereoselective hydride migration onto both the Ir[pb2]C bonds of 6 to give a kinetic mixture (6:1 ratio) of the isomeric adducts [(TpMe2)Ir{C1H(Et)C(R)=C(R)C(R)=C5(R)}(MeCN)(Ir–C5)] (9) and [(TpMe2)Ir{C1H(R)C(R)=C(R)C(R)=C5(Et)}(MeCN)(Ir–C5)] (10), with the latter being the thermodynamically preferred product. In contrast, complex 13 is stable in acetonitrile up to 100 °C, where it mainly experiences ring fragmentation to give the iridacyclopentadiene 1‐H as its MeCN adduct. All new compounds have been fully characterised by microanalysis and spectroscopy. Additionally, the solid‐state structures of 5, 6 and 13 have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Reaction Of Complex 1 With Propenementioning

confidence: 80%

Section: (R)=c(r)c(r)=c 4 (R)}(h 2 O)-(ir-cmentioning

confidence: 99%

Section: -(R)=c(h)c(r)=cunclassified

Section: Reaction Of Complex 1 With Propenementioning

confidence: 99%

Section: Reaction Of Complex 1 With Propenementioning

confidence: 99%

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