Exploiting Non‐Innocent Ligands to Prepare Masked Palladium(0) Complexes

Schuldig der Anklage, so lautet das Urteil für den anionischen Iridium‐Komplex [Ir(bpa−2 H)(cod)]− in Reaktionen mit Palladium(II)‐Verbindungen. Der Transfer von zwei Elektronen vom Ir‐Komplex zu Pd ermöglicht die einfache Herstellung von zwei‐ und dreikernigen π‐Imin‐koordinierten Pd0‐Verbindungen wie [{Ir(PyCH2NCHPy)(cod)}2Pd] (siehe Bild; C weiß, Ir rot, N blau, Pd gelb). bpa−2 H: doppelt deprotoniertes N,N‐Bis(2‐picolyl)amin (bpa); cod: 1,5‐Cyclooctadien.

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

Tejel

Asensio

Rı́o

et al. 2011

Angewandte Chemie

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C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands

et al. 2016

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The reactivity of a stable copper(II) complex bearing fully oxidized iminobenzoquinone redox ligands towards nucleophiles is described. In sharp contrast with its genuine low‐valent counterpart bearing reduced ligands, this complex performs high‐yielding C−N bond formations. Mechanistic studies suggest that this behavior could stem from a mechanism akin to reductive elimination occurring at the metal center but facilitated by the ligand: it is proposed that a masked high oxidation state of the metal can be stabilized as a lower copper(II) oxidation state by the redox ligands without forfeiting its ability to behave as a high‐valent copper(III) center. These observations are substantiated by a combination of advanced EPR spectroscopy techniques with DFT studies. This work sheds light on the potential of redox ligands as promoters of unusual reactivities at metal centers and illustrates the concept of masked high‐valent metallic species.

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

et al. 2011

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Guilty as charged is the verdict for anionic Ir complex [Ir(bpa−2 H)(cod)]− in its reactions with PdII compounds. The net transfer of two electrons from the Ir complex to Pd allows easy preparation of di‐ and trinuclear π‐imine‐coordinated Pd0 compounds such as [{Ir(PyCH2NCHPy)(cod)}2Pd] (see picture; C white, Ir red, N blue, Pd yellow). bpa−2 H: doubly deprotonated form of N,N‐bis(2‐picolyl)amine (bpa); cod: 1,5‐cyclooctadiene.

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Exploiting Non‐Innocent Ligands to Prepare Masked Palladium(0) Complexes

Cited by 6 publications

References 50 publications

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

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

C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands

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

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Exploiting Non‐Innocent Ligands to Prepare Masked Palladium(0) Complexes

Cited by 6 publications

References 50 publications

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

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

C−N Bond Formation from a Masked High‐Valent Copper Complex Stabilized by Redox Non‐Innocent Ligands

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

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

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

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