The migratory insertion of carbon monoxide in pentamethylcyclopentadienyliridium (III) complexes. Structural effects on reactivity and mechanism for rhodium and iridium systems
Identifieur interne : 004253 ( Istex/Curation ); précédent : 004252; suivant : 004254The migratory insertion of carbon monoxide in pentamethylcyclopentadienyliridium (III) complexes. Structural effects on reactivity and mechanism for rhodium and iridium systems
Auteurs : Donato Monti [Italie] ; Giuseppe Frachey [Italie] ; Mauro Bassetti [Italie] ; Anthony Haynes [Royaume-Uni] ; Glenn J. Sunley [Royaume-Uni] ; Peter M. Maitlis [Royaume-Uni] ; Andrea Cantoni [Italie] ; Gabriele Bocelli [Italie]Source :
- Inorganica Chimica Acta [ 0020-1693 ] ; 1995.
Abstract
The reactions of complex (C5Me5)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh2, PMePh2, PMe2Ph) give the products of alkyl migratory insertion (C5Me5Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C5Me5)Ir(Cl)(CO)(Ph) or the iodide complexes (C5Me5)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C5Me5)Ir(Cl)(CO)(Me) with PMePh2 and PMe2Ph in acetonitrile yields the chloride substitution product [(C5Me5)Ir(CO)(L)(Me)]+Cl−. Kinetic measurements for the reactions of (C5Me5)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C5Me5)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step (K = 1.5 (CyNC), 7.3 (PHPh2), 7.1 (PMePh2) dm3 mol−1 at 323 K) and k2 for the slow carboncarbon bond formation (k2 (105) = 6.9 (CyNC), 1.2 (PHPh2), 1.0 (PMePh2) s−1 at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh2 obtained between 308 and 338 K, are ΔH≠ = 106±16 kJ mol−1 and ΔS≠ = − 14±5 J K−1 mol−1. The reaction of 1a with PMePh2 proceeds at similar rates in tetrahydrofuran (K = 3.7 dm3 mol−1, k2 (105) = 1.2 s−1, 323 K). The crystal structure of (C5Me5)Ir(Cl)(COMe) (PMe2Ph) has been determined by X-ray diffraction. C20H29ClOPIr: Mr = 544.1, monoclinic, P21/n, a = 8.084 (2), b = 9.030(2), c = 28.715 (3) A ̊, β = 91.41 (3)°, Z = 4, Dc = 1.71 g cm−3, V = 2095.5 Å3, room temperatyre, Mo Kα, γ = 0.71069, μ = 65.55 cm−1, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η5-C5Me5 molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the IrP and the IrCOMe bonds are eclipsed with respect to C(ring)-methyl bonds.
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DOI: 10.1016/0020-1693(95)04573-2
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Mauro Bassetti<affiliation><mods:affiliation>Corresponding author.</mods:affiliation>
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<affiliation wicri:level="1"><mods:affiliation>Department of Chemistry, The University, Sheffield S3 7HF, UK</mods:affiliation>
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<front><div type="abstract" xml:lang="en">The reactions of complex (C5Me5)Ir(Cl) (CO) (Me) (1a) with cyclohexylisocyanide and phosphines (L=CyNC, PHPh2, PMePh2, PMe2Ph) give the products of alkyl migratory insertion (C5Me5Ir(Cl) (COMe) (L), in toluence or tetrahydrofuran at 323 K or higher temperature. The phenyl analogue (C5Me5)Ir(Cl)(CO)(Ph) or the iodide complexes (C5Me5)Ir(I) (CO) (R) (R=Me, Ph_are not reactive under the same conditions. The reaction of (C5Me5)Ir(Cl)(CO)(Me) with PMePh2 and PMe2Ph in acetonitrile yields the chloride substitution product [(C5Me5)Ir(CO)(L)(Me)]+Cl−. Kinetic measurements for the reactions of (C5Me5)Ir(Cl)(CO)(Me) in toluene are first order in the iridium complex and exhibit a saturation dependence on the incoming donors L. Analysis of the data suggests a two-step process involving (i) rapid formation of a molecular complex [(C5Me5)Ir(Cl)(CO)(Me), (L)], in which the structure of 1a is unperturbed within the limits of spectroscopic analysis, and (ii) rate determining methyl migration. The reaction parameters are K for the pre-equilibrium step (K = 1.5 (CyNC), 7.3 (PHPh2), 7.1 (PMePh2) dm3 mol−1 at 323 K) and k2 for the slow carboncarbon bond formation (k2 (105) = 6.9 (CyNC), 1.2 (PHPh2), 1.0 (PMePh2) s−1 at 323 K). The activation parameters for the methyl migration step in the reaction with PMePh2 obtained between 308 and 338 K, are ΔH≠ = 106±16 kJ mol−1 and ΔS≠ = − 14±5 J K−1 mol−1. The reaction of 1a with PMePh2 proceeds at similar rates in tetrahydrofuran (K = 3.7 dm3 mol−1, k2 (105) = 1.2 s−1, 323 K). The crystal structure of (C5Me5)Ir(Cl)(COMe) (PMe2Ph) has been determined by X-ray diffraction. C20H29ClOPIr: Mr = 544.1, monoclinic, P21/n, a = 8.084 (2), b = 9.030(2), c = 28.715 (3) A ̊, β = 91.41 (3)°, Z = 4, Dc = 1.71 g cm−3, V = 2095.5 Å3, room temperatyre, Mo Kα, γ = 0.71069, μ = 65.55 cm−1, F(000) = 1044, R = 0.037 for 2453 independent observed reflections. The complex shows a deformed tetrahedral coordination assuming the η5-C5Me5 molecular fragment as a single coordination site. The iridium-chlorine bond is staggered with respect to two adjacent C(ring)-methyl bonds, while the IrP and the IrCOMe bonds are eclipsed with respect to C(ring)-methyl bonds.</div>
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