Di-μ-chlorobis(1,5-cyclooctadiene)diiridium(I)

Westcott, Stephen A.; Parthasarathy, Saravanan

doi:10.1002/047084289x.rd089m.pub2

Cited by 2 publications

(1 citation statement)

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“…These dimers have important industrial applications as catalysts and catalyst precursors, and as such, make good model compounds. [Ir(COD)Cl] 2 is routinely used as a catalyst in carbon–carbon and carbon–heteroatom bond formations, in addition to alkylation, hydrogenation, and hydroamination reactions. , It is also commonly used as a precursor to Crabtree’s catalysts . [Rh(COD)Cl] 2 is used for carbon–carbon/heteroatom formation and has further applications as a precursor in hydrogenation and cross-coupling reactions …”

Section: Introductionmentioning

confidence: 99%

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

et al. 2021

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X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray–matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl]2 and [Rh(COD)Cl]2, exposed to radiation in X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiments. From these complementary techniques, changes to structure, chemical environments, and electronic structure are observed as a function of X-ray exposure, allowing comparisons of stability to be made between the two catalysts. Radiation dose is estimated using recent developments to the RADDOSE-3D software for small molecules and applied to powder XRD and XPS experiments. Further insights into the electronic structure of the catalysts and changes occurring as a result of the irradiation are drawn from density functional theory (DFT). The techniques combined here offer much needed insight into the X-ray-induced effects in transition-metal catalysts and, consequently, their intrinsic stabilities. There is enormous potential to extend the application of these methods to other small molecular systems of scientific or industrial relevance.

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Section: Introductionmentioning

confidence: 99%

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

et al. 2021

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Synthesis and Structures of Rh^I and Ir^I Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts

Doddi

Bockfeld

Tamm

2018

Zeitschrift anorg allge chemie

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N-Heterocyclic carbene-phosphinidene adducts of the type (IDipp)PR [R = Ph (5), SiMe 3 (6); IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] were used as ligands for the preparation of rhodium(I) and iridium(I) complexes. Treatment of (IDipp)PPh (5) with the dimeric complexes [M(μ-Cl)(COD)] 2 (M = Rh, Ir; COD = 1,5-cyclcooctadiene) afforded the corresponding metal(I) complexes [M(COD)Cl{(IDipp)PPh}] [M = Rh (7) or Ir (8)] in moderate to good yields. The reaction of (IDipp)PSiMe 3 (6) with [Ir(μ-Cl)(COD)] 2 did 44 not yield trimethylsilyl chloride elimination product, but furnished the 1:1 complex, [Ir(COD)Cl{(IDipp)PSiMe 3 }] (9). Additionally, the rhodium-COD complex 7 was converted into the corresponding rhodiumcarbonyl complex [Rh(CO) 2 Cl{(IDipp)PPh}] (10) by reaction with an excess of carbon monoxide gas. All complexes were fully characterized by NMR spectroscopy, microanalyses, and single-crystal X-ray diffraction studies.

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Di-μ-chlorobis(1,5-cyclooctadiene)diiridium(I)

Cited by 2 publications

References 49 publications

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

Synthesis and Structures of Rh^I and Ir^I Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts

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Di-μ-chlorobis(1,5-cyclooctadiene)diiridium(I)

Cited by 2 publications

References 49 publications

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]2Catalysts

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]2Catalysts

Synthesis and Structures of RhI and IrI Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts

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Product

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Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl]₂Catalysts

Synthesis and Structures of Rh^I and Ir^I Complexes Supported by N‐Heterocyclic Carbene‐Phosphinidene Adducts