Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to IrI/Pd0 and IrI/Pd0/IrI Cores

Tejel, Cristina; Asensio, Laura; Rı́o, M. Pilar del; Bruin, Bas de; López, José A.; Ciriano, Miguel A.

doi:10.1002/anie.201104045

Cited by 22 publications

(12 citation statements)

References 90 publications

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“…of potassium tert ‐butoxide in THF, however, affords only monodeprotonated chlorido carbonyl iron complex 3a derived from an intramolecular hydride transfer. Similar intramolecular hydride migration in redox‐active ligands has been observed in the corresponding rhodium and palladium complexes . Interestingly, the addition of more equivalents of KO t Bu did not lead to further deprotonation.…”

Section: Resultssupporting

confidence: 69%

The Stabilization Effect of π‐Backdonation Ligands on the Catalytic Reactivities of Amido‐Ene(amido) Iron Catalysts in the Asymmetric Transfer Hydrogenation of Ketones

Xue

Wang

et al. 2020

Eur J Inorg Chem

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A series of P–N–N–P iron complexes (1–3) were synthesized, characterized, and tested for their catalytic activities to explore the structure‐performance relationship of the catalyst precursors and intermediates. While the amino(imno) carbonyl complex (1) was highly active, the bis(amino) (2) and pyridyl‐amino (3) analogues were inactive. Stoichiometric reactions were studied to elucidate the mechanistic causes of the success and failure of these iron catalysts. Although 1a and 1b are active and stable at room temperature, 2a was found to be highly unstable under the catalytic conditions. Further electronic studies on 1a, 1b and 2a revealed that the π‐backdonation interactions in 1a and 1b can delocalize the electron density on the iron centers to the π‐bound ligand, explaining the elevated stability of the ene(amido)‐containing catalytic intermediates. Dearomatized pyridyl iron complexes (3b) were also inactive because they were too basic to be stable in the reaction solution.

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Section: Resultssupporting

confidence: 69%

The Stabilization Effect of π‐Backdonation Ligands on the Catalytic Reactivities of Amido‐Ene(amido) Iron Catalysts in the Asymmetric Transfer Hydrogenation of Ketones

Xue

Wang

et al. 2020

Eur J Inorg Chem

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“…2.31 Å; Pt: 2.27 Å) complexes. 21,22 The bridging M-Ga bond lengths of 1a (a.v. 2.48 Å) and 1b (a.v.…”

Section: Resultsmentioning

confidence: 99%

Organogallium- and organozinc-rich palladium and platinum clusters

2014

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The heteroleptic, binuclear compounds [M2(GaCp*)3(PMe3)2] (M = Pd: 1a, Pt: 1b, Cp* = pentamethylcyclopentadienyl) can be obtained if [Pd2(dvds)3] (dvds = 1,3-divinyl-1,1,3,3-tetramethyldisiloxane) or [Pt(COD)2] (COD = cyclooctadiene) were treated with a 3 : 2 ratio of GaCp* and PMe3. A trinuclear complex [Pd3(GaCp*)3(PMe3)3] (2) was isolated from in situ prepared [Pd(PMe3)2Me2] and treatment with GaCp*. The new complexes were used as starting compounds for selective Ga/Zn exchange reactions to afford the dinuclear palladium compound [Pd2(ZnCp*)(ZnMe)3(PMe3)5] (3a) and the mononuclear platinum compound [Pt(ZnCp*)2(ZnMe)2(PMe3)2] (3b). The effects of a final transition metal count in organozinc ligated compounds and stabilization of Lewis acidic fragments like [Pd(PPh3)3], [Ni(C2H4)3] or [Mo(CO)5] were presented and discussed. All compounds have been fully characterized by (1)H, (13)C, and (31)P NMR spectroscopy, mass spectrometry using a liquid injection field desorption ionization (LIFDI) method, elemental analysis, and single crystal X-ray diffraction studies and the coordination polyhedra were analysed by the method of continuous shape measure (CShM).

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“…24 There is one example of a structurally characterised imine complex of Pd 0 . 25 The coordination of aldehydes and ketones to Ni 0 has been studied in depth by Love and Kennepohl, using a variety of experimental and computational techniques. 26,27 All of the η 2 -complexes A′ in this work are square planar; attempts to locate tetrahedral complexes were unsuccessful, with the structure optimising to the square planar geometry in each case.…”

Section: Paper Syn Thesismentioning

confidence: 99%

Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes

2019

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A detailed comparison of the effect of coordinating functional groups on the performance of Suzuki–Miyaura reactions catalysed by nickel and palladium is reported, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.

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Developing Synthetic Approaches with Non‐Innocent Metalloligands: Easy Access to Ir^I/Pd⁰ and Ir^I/Pd⁰/Ir^I Cores

Cited by 22 publications

References 90 publications

The Stabilization Effect of π‐Backdonation Ligands on the Catalytic Reactivities of Amido‐Ene(amido) Iron Catalysts in the Asymmetric Transfer Hydrogenation of Ketones

The Stabilization Effect of π‐Backdonation Ligands on the Catalytic Reactivities of Amido‐Ene(amido) Iron Catalysts in the Asymmetric Transfer Hydrogenation of Ketones

Organogallium- and organozinc-rich palladium and platinum clusters

Nickel versus Palladium in Cross-Coupling Catalysis: On the Role of Substrate Coordination to Zerovalent Metal Complexes

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