Inner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complex

Handle URI:
http://hdl.handle.net/10754/625693
Title:
Inner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complex
Authors:
Veenboer, Richard M. P. ( 0000-0002-4878-580X ) ; Collado, Alba; Dupuy, Stéphanie; Lebl, Tomas ( 0000-0002-0269-3221 ) ; Falivene, Laura ( 0000-0003-1509-6191 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Cordes, David B.; Slawin, Alexandra M. Z.; Cazin, Catherine S. J. ( 0000-0002-9094-8131 ) ; Nolan, Steven P. ( 0000-0001-9024-2035 )
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 IPrCl-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 IPrCl-gold(I) fragment behavior similar to that of related systems.
KAUST Department:
Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia
Citation:
Veenboer RMP, Collado A, Dupuy S, Lebl T, Falivene L, et al. (2017) Inner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complex. Organometallics 36: 2861–2869. Available: http://dx.doi.org/10.1021/acs.organomet.7b00345.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
20-Jul-2017
DOI:
10.1021/acs.organomet.7b00345
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
The European Research Council (ERC) and the Engineering and Physical Sciences Research Council (EPSRC) are gratefully acknowledged for their support. S.P.N. and L.C. thank King Abdullah University of Science and Technology (KAUST) for support. Dr. Filippo Stella is thanked for his help with NMR experiments. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974-03.
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00345
Appears in Collections:
Articles

Full metadata record

DC FieldValue Language
dc.contributor.authorVeenboer, Richard M. P.en
dc.contributor.authorCollado, Albaen
dc.contributor.authorDupuy, Stéphanieen
dc.contributor.authorLebl, Tomasen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorCordes, David B.en
dc.contributor.authorSlawin, Alexandra M. Z.en
dc.contributor.authorCazin, Catherine S. J.en
dc.contributor.authorNolan, Steven P.en
dc.date.accessioned2017-10-03T12:49:34Z-
dc.date.available2017-10-03T12:49:34Z-
dc.date.issued2017-07-20en
dc.identifier.citationVeenboer RMP, Collado A, Dupuy S, Lebl T, Falivene L, et al. (2017) Inner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complex. Organometallics 36: 2861–2869. Available: http://dx.doi.org/10.1021/acs.organomet.7b00345.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/acs.organomet.7b00345en
dc.identifier.urihttp://hdl.handle.net/10754/625693-
dc.description.abstractThe 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 IPrCl-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 IPrCl-gold(I) fragment behavior similar to that of related systems.en
dc.description.sponsorshipThe European Research Council (ERC) and the Engineering and Physical Sciences Research Council (EPSRC) are gratefully acknowledged for their support. S.P.N. and L.C. thank King Abdullah University of Science and Technology (KAUST) for support. Dr. Filippo Stella is thanked for his help with NMR experiments. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974-03.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.organomet.7b00345en
dc.titleInner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complexen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabiaen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionEaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, United Kingdomen
dc.contributor.institutionEaStCHEM, School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, United Kingdomen
dc.contributor.institutionDepartment of Inorganic and Physical Chemistry, Ghent University, Building S3, Krijgslaan 281, 9000 Gent, Belgiumen
dc.contributor.institutionDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabiaen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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