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Pincerlike Cyclic Systems for Unraveling Fundamental Coinage Metal Redox Processes

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The Privileged Pincer-Metal Platform: Coordination Chemistry & Applications

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 54))

Abstract

Pincerlike cyclic ligands have overcome the high instability of transition metals in their higher oxidation states and have permitted the isolation of such species and the exhaustive study of their properties and reactivity. The formation and isolation of organometallic CuII and MIII (M=Cu, Ag, Au) complexes stabilized by NCPs, carbaporphyrins, carbaporphyrinoids, heterocalixarenes, and triaza macrocyclic ligands will be discussed in this chapter. The study of these complexes have led to the discovery of unprecedented reactivity and proved the plausibility of often invoked pathways in copper-catalyzed cross-coupling reactions. Aryl-MIII (M=Cu, Ag) stable species have been implicated as the key intermediate species that operate in coupling catalysis through two-electron redox cycles involving oxidative addition and reductive elimination fundamental steps.

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Abbreviations

Ac:

Acetyl

Ar:

Aryl

AT:

Atom transfer

cal:

Calories

cat:

Catalytic

Cp:

Cyclopentadienyl

DDQ:

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

DFT:

Density functional theory

DMF:

Dimethylformamide

DMSO:

Dimethyl sulfoxide

equiv:

Equivalent(s)

Et:

Ethyl

h:

Hour(s)

i-Bu:

Isobutyl

L:

Ligand

Me:

Methyl

min:

Minute(s)

mol:

Mole(s)

N2CP:

Doubly N-confused porphyrin

Naph:

Naphthalene

n-Bu:

Butyl

NCP:

N-confused porphyrin

NMR:

Nuclear magnetic resonance

n-Pr:

Propyl

Nuc:

Nucleophile

[O]:

Oxidant

Ph:

Phenyl

phen:

Phenanthroline

py:

Pyridine

rt:

Room temperature

s:

Second(s)

SET:

Single-electron transfer

t-Bu:

Tert-butyl

TEMPO:

(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl

Tf:

Trifluoromethanesulfonyl (triflyl)

TFA:

Trifluoroacetic acid

THF:

Tetrahydrofuran

Tol:

4-Methylphenyl

UV–Vis:

Ultraviolet–visible spectroscopy

V:

Volt(s)

xyl:

Xylyl

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Authors and Affiliations

  1. QBIS-CAT Research Group, Institut de Química Computacional i Catàlisi (IQCC), Girona, 17071, Catalonia, Spain

    Marc Font & Xavi Ribas

  2. Departament de Química, Universitat de Girona, Campus Montilivi, Girona, 17071, Catalonia, Spain

    Marc Font & Xavi Ribas

Authors
  1. Marc Font
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  2. Xavi Ribas
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Correspondence to Xavi Ribas .

Editor information

Editors and Affiliations

  1. Organic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands

    Gerard van Koten

  2. Department of Chemistry & Biology, Ryerson University, Toronto, Canada

    Robert A Gossage

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Font, M., Ribas, X. (2015). Pincerlike Cyclic Systems for Unraveling Fundamental Coinage Metal Redox Processes. In: van Koten, G., Gossage, R. (eds) The Privileged Pincer-Metal Platform: Coordination Chemistry & Applications. Topics in Organometallic Chemistry, vol 54. Springer, Cham. https://doi.org/10.1007/3418_2015_112

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