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Inner-sphere versus outer-sphere coordination of BF4- in a NHC-gold(I) complex

Richard MP Veenboer, Alba Collado, Stéphanie Dupuy, Tomas Lebl, Laura Falivene, Luigi Cavallo, David B Cordes, Alexandra MZ Slawin, Catherine Cazin UGent and Steven Nolan UGent (2017) ORGANOMETALLICS. 36(15). p.2861-2869
abstract
The role of counterions in chemistry mediated by gold complexes stretches much further than merely providing charge balance to cationic gold species. Interplay between their basicities and coordination strengths influences interactions with both the gold center and substrates in catalysis. Actual monogold-(I) active species are generally believed to be monocoordinated species, formed from the abstraction or the decoordination of a second ligand from precursor complexes, but only a small amount of experimental evidence exists to underpin the existence of these transient species. The formation of a bench-stable neutral IPrCI-gold(I) tetrafluoroborate complex is reported herein. Experimental studies by X-ray diffraction analysis and NMR spectroscopy and theoretical studies by DFT calculations were conducted to determine the composition, structure, and behavior of this complex. The absence of an auxiliary ligand resulted in inner-sphere coordination of the counterion in the solid state. In solution, an equilibrium between two conformations was found with the counterion occupying inner-sphere and outer-sphere positions, respectively. Stoichiometric and catalytic reactivity studies with the tetrafluoroborate complex have been conducted. These confirmed the lability of the inner-sphere coordinating counterion that gives the IPrCI-gold(I) fragment behavior similar to that of related systems.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
N-HETEROCYCLIC CARBENE, SILVER-FREE PROTOCOLS, GOLD CATALYSIS, GOLD(III) COMPLEXES, REACTION-MECHANISM, HIGHLY EFFICIENT, STEREOSELECTIVE HYDROCARBOXYLATION, ALKYNES, COUNTERION, NHC
journal title
ORGANOMETALLICS
Organometallics
volume
36
issue
15
pages
2861 - 2869
Web of Science type
Article
Web of Science id
000407869100019
ISSN
0276-7333
1520-6041
DOI
10.1021/acs.organomet.7b00345
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
8536737
handle
http://hdl.handle.net/1854/LU-8536737
date created
2017-11-09 11:41:55
date last changed
2017-12-05 15:21:41
@article{8536737,
  abstract     = {The role of counterions in chemistry mediated by gold complexes stretches much further than merely providing charge balance to cationic gold species. Interplay between their basicities and coordination strengths influences interactions with both the gold center and substrates in catalysis. Actual monogold-(I) active species are generally believed to be monocoordinated species, formed from the abstraction or the decoordination of a second ligand from precursor complexes, but only a small amount of experimental evidence exists to underpin the existence of these transient species. The formation of a bench-stable neutral IPrCI-gold(I) tetrafluoroborate complex is reported herein. Experimental studies by X-ray diffraction analysis and NMR spectroscopy and theoretical studies by DFT calculations were conducted to determine the composition, structure, and behavior of this complex. The absence of an auxiliary ligand resulted in inner-sphere coordination of the counterion in the solid state. In solution, an equilibrium between two conformations was found with the counterion occupying inner-sphere and outer-sphere positions, respectively. Stoichiometric and catalytic reactivity studies with the tetrafluoroborate complex have been conducted. These confirmed the lability of the inner-sphere coordinating counterion that gives the IPrCI-gold(I) fragment behavior similar to that of related systems.},
  author       = {Veenboer, Richard MP and Collado, Alba and Dupuy, St{\'e}phanie and Lebl, Tomas and Falivene, Laura and Cavallo, Luigi and Cordes, David B and Slawin, Alexandra MZ and Cazin, Catherine and Nolan, Steven},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keyword      = {N-HETEROCYCLIC CARBENE,SILVER-FREE PROTOCOLS,GOLD CATALYSIS,GOLD(III) COMPLEXES,REACTION-MECHANISM,HIGHLY EFFICIENT,STEREOSELECTIVE HYDROCARBOXYLATION,ALKYNES,COUNTERION,NHC},
  language     = {eng},
  number       = {15},
  pages        = {2861--2869},
  title        = {Inner-sphere versus outer-sphere coordination of BF4- in a NHC-gold(I) complex},
  url          = {http://dx.doi.org/10.1021/acs.organomet.7b00345},
  volume       = {36},
  year         = {2017},
}

Chicago
Veenboer, Richard MP, Alba Collado, Stéphanie Dupuy, Tomas Lebl, Laura Falivene, Luigi Cavallo, David B Cordes, Alexandra MZ Slawin, Catherine Cazin, and Steven Nolan. 2017. “Inner-sphere Versus Outer-sphere Coordination of BF4- in a NHC-gold(I) Complex.” Organometallics 36 (15): 2861–2869.
APA
Veenboer, R. M., Collado, A., Dupuy, S., Lebl, T., Falivene, L., Cavallo, L., Cordes, D. B., et al. (2017). Inner-sphere versus outer-sphere coordination of BF4- in a NHC-gold(I) complex. ORGANOMETALLICS, 36(15), 2861–2869.
Vancouver
1.
Veenboer RM, Collado A, Dupuy S, Lebl T, Falivene L, Cavallo L, et al. Inner-sphere versus outer-sphere coordination of BF4- in a NHC-gold(I) complex. ORGANOMETALLICS. 2017;36(15):2861–9.
MLA
Veenboer, Richard MP, Alba Collado, Stéphanie Dupuy, et al. “Inner-sphere Versus Outer-sphere Coordination of BF4- in a NHC-gold(I) Complex.” ORGANOMETALLICS 36.15 (2017): 2861–2869. Print.