Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II)

Atanu K. Das, Mark H. Engelhard, Sheri Lense, John Roberts, R Morris Bullock

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Covalent tethering of PPh 2NC6H4C≡CH 2 ligands (PPh 2NC6H4C≡CH 2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a CuI-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [NiII(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents NiII per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, PPh 2NPh 2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [NiII(diphosphine)2]2+ complex.

Original languageEnglish
Pages (from-to)12225-12233
Number of pages9
JournalDalton Transactions
Volume44
Issue number27
DOIs
Publication statusPublished - Jul 21 2015

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Alkynes
Azides
Cycloaddition
Glassy carbon
Ligands
Electrodes
Photoelectrons
Carbon
X rays

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II). / Das, Atanu K.; Engelhard, Mark H.; Lense, Sheri; Roberts, John; Bullock, R Morris.

In: Dalton Transactions, Vol. 44, No. 27, 21.07.2015, p. 12225-12233.

Research output: Contribution to journalArticle

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