Chemistry Surrounding Monomeric Copper(l) Methyl, Phenyl, Anilido, Ethoxide, and Phenoxide Complexes Supported by N-Heterocyclic Carbene Ligands: Reactivity Consistent with Both Early and Late Transition Metal Systems

Description:

Article on chemistry surrounding monomeric copper(I) methyl, phenyl, anilido, ethoxide, and phenoxide complexes supported by N-heterocyclic carbene ligands.

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Creation Date: September 27, 2006
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UNT College of Arts and Sciences
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UNT Scholarly Works
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Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: September 27, 2006
Description:

Article on chemistry surrounding monomeric copper(I) methyl, phenyl, anilido, ethoxide, and phenoxide complexes supported by N-heterocyclic carbene ligands.

Degree:
Department: Chemistry
Note:

Reprinted with permission from Inorganic Chemistry. Copyright 2006 American Chemical Society.

Note:

Abstract: Monomeric copper(l) alkyl complexes that possess the N-heterocyclic carbene (NHC) ligands IPr, SIPr, and IMes [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] react with amines or alcohols to release alkane and form the corresponding monomeric copper(l) amido, alkoxide, or aryloxide complexes. Thermal decomposition reactions of (NHC)Cu׀ methyl complexes at temperatures between 100 and 130 °C produce methane, ethane, and ethylene. The reactions of (NHC)Cu(NHPh) complexes with bromoethane reveal increasing nucleophilic reactivity at the anilido ligand in the order (SIPR)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh) [dtbpe = 1,2-bis(di-tert-butylphosphino)ethane]. DFT calculations suggest that the HOMO for the series of Cu anilido complexes is localized primarily on the amido nitrogen with some pπanilido-dπCu π*-character. [(IPr)Cu(μ-H)]2 and (IPr)Cu(Ph) react with aniline to quantitatively produce (IPr)Cu(NHPh)/dihydrogen and (IPr)Cu(NHPh)/benzene, respectively. Analysis of the DFT calculations reveals that the conversion of [(IPr)Cu(μ-H)]2 and aniline to (IPr)Cu(NHPh) and dihydrogen is favorable with ∆H ≈ -7 kcal/mol and ∆G ≈ -9 kcal/mol.

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14 p.

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Subject(s):
Keyword(s): monomeric copper | transition metal systems
Source: Inorganic Chemistry, 2006, Washington DC: American Chemical Society, pp. 9032-9045
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ic0611995
  • ARK: ark:/67531/metadc77128
Resource Type: Article
Format: Text
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Access: Public
Citation:
Publication Title: Inorganic Chemistry
Volume: 45
Issue: 22
Page Start: 9032
Page End: 9045
Pages: 14
Peer Reviewed: Yes