What question did this study set out to answer?

To elucidate the mechanisms, kinetics, and structural intermediates involved in the insertion of allenes into palladium–carbon bonds of complexes supported by bidentate nitrogen ligands.

February 1, 1997OrganometallicsOpen Access

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

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Authors

JDJohannes G. P. DelisUtrecht University JGJ.H. GroenUtrecht University KVKees VriezeRadboud University Nijmegen

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Implication

Kinetic and structural study demonstrates ligand-dependent pathways during allene insertion into palladium–carbon bonds, indicating that group migration is the rate-determining step.

Key Points

To elucidate the mechanisms, kinetics, and structural intermediates involved in the insertion of allenes into palladium–carbon bonds of complexes supported by bidentate nitrogen ligands.
Determined solid-state and solution structures of (N⌒N)Pd(R)X complexes using X-ray crystallography and nuclear Overhauser effect (NOE) NMR spectroscopy across polar and apolar solvents.
Conducted kinetic analyses measuring insertion rates of propadiene and 1,2-heptadiene under varying concentrations of palladium, allene, added free nitrogen ligands, and halide salts (Cl⁻, Br⁻).
Reactions display first-order dependence on palladium concentration and proceed through both allene-dependent and allene-independent pathways, with alkyl or acyl group migration identified as the rate-determining step.
Flexible bidentate ligands accelerate insertion rates by readily dissociating a single nitrogen donor to expose a vacant coordination site, whereas excess free ligand retards the reaction.
Excess halide ions unexpectedly accelerated reaction rates for specific methyl and acyl palladium complexes rather than causing mass-law retardation.

Cite This Study

Delis et al. (1997) studied this question.

synapsesocial.com/papers/6a94d02aabd4c05a5bf57789 https://doi.org/10.1021/om960790e

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Implication

Kinetic and structural study demonstrates ligand-dependent pathways during allene insertion into palladium–carbon bonds, indicating that group migration is the rate-determining step.

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

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Member takes

Implication

Key Points

Cite This Study

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Discussion

Member takes

Implication

Key Points

Cite This Study

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