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 language | English |
|---|---|
| Pages (from-to) | 12225-12233 |
| Number of pages | 9 |
| Journal | Dalton Transactions |
| Volume | 44 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - Jul 21 2015 |
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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 journal › Article
}
TY - JOUR
T1 - Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II)
AU - Das, Atanu K.
AU - Engelhard, Mark H.
AU - Lense, Sheri
AU - Roberts, John
AU - Bullock, R Morris
PY - 2015/7/21
Y1 - 2015/7/21
N2 - 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.
AB - 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.
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UR - http://www.scopus.com/inward/citedby.url?scp=84953911235&partnerID=8YFLogxK
U2 - 10.1039/c5dt00162e
DO - 10.1039/c5dt00162e
M3 - Article
VL - 44
SP - 12225
EP - 12233
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 27
ER -