Facile Intermolecular Phosphine Ligand Exchange Reactions Between Square Planar Iridium and Platinum Centers

Rominger, Robert L.; McFarland, Jeffrey M.; Jeitler, James R.; Thompson, Jeffrey S.; Atwood, Jim D.

doi:10.1080/00958979408022540

Cited by 9 publications

(3 citation statements)

References 14 publications

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“…6). This scrambling of PR 3 -type ligands between iridium-centred square-planar complexes has been observed previously by Rominger et al , 72 who noted that this process occurs rapidly, with an equilibrium distribution of phosphine ligands being observed within minutes at −70 °C. Within the equilibrium mixture, each complex is able to react irreversibly with p H 2 to form three unique hyperpolarised dihydride complexes (shown in Fig.…”

Section: Resultssupporting

confidence: 83%

Quantitative reaction monitoring using parahydrogen-enhanced benchtop NMR spectroscopy

Robinson,

Hill-Casey,

Duckett

et al. 2024

Phys. Chem. Chem. Phys.

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Section: Resultssupporting

confidence: 83%

Quantitative reaction monitoring using parahydrogen-enhanced benchtop NMR spectroscopy

Robinson,

Hill-Casey,

Duckett

et al. 2024

Phys. Chem. Chem. Phys.

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“…15,16 Additionally, an Ir(I) Vaska system undergoes ligand dissociation in phosphine-ligand redistribution reactions. 17,18 With Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), 19 gas-phase ion-molecule reaction rate constants and equilibria are readily determined. [20][21][22][23][24][25] Most prior FT-ICR MS analysis of gasphase metal ion-molecule reactions has been based on ions generated by electron ionization of volatile metal complexes or laser desorption/ionization to generate metal ions directly.…”

Section: Introductionmentioning

confidence: 99%

“…There are rare exceptions to this mechanism, notably Pt(H 2 O) 4 2+ exchanging a water for halide. That reaction proceeds by dissociative interchange: the Pt(H 2 O) 4 2+ complex loses water to give Pt(H 2 O) 3 2+ and then binds the incoming halide to form Pt(H 2 O) 3 X + . , Additionally, an Ir(I) Vaska system undergoes ligand dissociation in phosphine-ligand redistribution reactions. , …”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Ligand Exchange in a Square-Planar Rhodium(I) Complex Proceeding by Dissociative Exchange: ESI FT-ICR MS and DFT Evidence

et al. 2003

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Although the kinetics of square-planar d8 ligand-substitution reactions have been explored extensively in solution, no such studies of gas-phase systems have been reported. Measurement of gas-phase ligand exchange offers the advantage that the exchange mechanism is readily determined in the absence of solvent effects. The complex trans-Rh(PPh3)2CO(4-picoline)+ substitutes pyridine for its 4-picoline ligand readily in the gas phase but also loses CO during the reaction. The double-resonance experiments show that its primary substitution pathway proceeds dissociatively, unlike almost all solution ligand substitutions for Pt(II) and Pd(II). The density functional calculations reveal that the bond energies of Rh-4-picoline, Rh-pyridine, and Rh−CO are similar enough that CO loss might be expected. In support of the dissociative mechanism, the calculations also show five-coordinate intermediates for the associative pathway to be relatively high in energy.

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Mechanisms of Reaction of Organometallic Complexes

Atwood

Rosenberg

2005

Encyclopedia of Inorganic Chemistry

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An overview of the mechanistic features of organometallic reactions is presented. The primary mechanistic types discussed are ligand substitution, oxidative addition, reductive elimination, and electron transfer. Each reaction pathway is discussed within the context of the common electron counts encountered for most organometallic complexes. Examples of how these common reaction pathways extend to polynuclear complexes are also presented. Although reasonable generalizations with regard to overall reaction rates and stepwise mechanisms using the electron count formalism can be made, many recent reports point out that the details of ligand and metal center structure can override these general trends. A considerable amount of quantitative rate data is provided and computational methodologies for understanding the observed rates are discussed.

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Facile Intermolecular Phosphine Ligand Exchange Reactions Between Square Planar Iridium and Platinum Centers

Cited by 9 publications

References 14 publications

Quantitative reaction monitoring using parahydrogen-enhanced benchtop NMR spectroscopy

Quantitative reaction monitoring using parahydrogen-enhanced benchtop NMR spectroscopy

Gas-Phase Ligand Exchange in a Square-Planar Rhodium(I) Complex Proceeding by Dissociative Exchange: ESI FT-ICR MS and DFT Evidence

Mechanisms of Reaction of Organometallic Complexes

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