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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...

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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

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Published on: July 30, 2017

An Isolable Mononuclear Palladium(I) Amido Complex.

Jian Liu¹, Melissa M Bollmeyer², Yujeong Kim^3,4

¹State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Journal of the American Chemical Society

|July 7, 2021

Summary

This summary is machine-generated.

Researchers isolated a novel Palladium(I) amido complex, [(BINAP)Pd(NHAr^Trip)], a key intermediate in catalysis. This discovery advances understanding of palladium chemistry and its catalytic applications.

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Published on: March 20, 2014

Area of Science:

Organometallic Chemistry
Catalysis
Inorganic Chemistry

Background:

Mononuclear Palladium(I) species are crucial but poorly understood intermediates in palladium-catalyzed reactions.
Limited accessibility hinders detailed study of these reactive species.

Purpose of the Study:

To isolate and characterize a stable mononuclear Palladium(I) amido complex.
To investigate the electronic structure and bonding of the Pd(I) amido species.
To explore the reactivity of the novel Palladium(I) complex.

Main Methods:

Synthesis of the Palladium(I) amido complex [(BINAP)Pd(NHAr^Trip)] from (BINAP)PdCl₂ and LiNHAr^Trip.
Characterization using X-ray crystallography, electron paramagnetic resonance (EPR), and multiedge Pd X-ray absorption spectroscopy (XAS).
Theoretical calculations to elucidate electronic structure and bonding interactions.

Main Results:

Successful isolation and full characterization of the mononuclear Pd(I) amido complex.
X-ray crystallography revealed the complex's structure.
Spectroscopic and theoretical studies indicated a stabilized Pd-N bond influenced by interligand dispersion forces despite Pauli repulsion.

Conclusions:

The study provides direct access to a previously elusive Pd(I) amido intermediate.
The findings offer insights into the stabilization mechanisms of Pd(I) species.
The characterized complex exhibits reactivity consistent with its electronic features, including homolytic Pd-N bond cleavage and amine deprotonation.