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Dinuclear gold(I) complexes bearing alkyl-bridged bis(N-heterocyclic carbene) ligands as catalysts for carboxylative cyclization of propargylamine : synthesis, structure, and kinetic and mechanistic comparison to the mononuclear complex [Au(IPr)CI]

(2020) ORGANOMETALLICS. 39(15). p.2907-2916
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Abstract
Eight new dinuclear gold(I) complexes, [Au-2(L)X-2] (1-8), were synthesized using a straightforward synthetic procedure under very mild conditions. The complexes have been characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray structure analysis. Their catalytic activity was investigated in the carboxylative cyclization of propargylamine (PPA). A superior performance in comparison to [Au(IPr)Cl] (9) was obtained for complexes 1 and 2 having an eight-methylene bridge connecting two NHCs with an arene bearing an isopropyl substituent for X = Cl, Br. This prompted more detailed kinetic and mechanistic studies by FTIR comparing dinuclear complex 2 of X = Cl to complex 9. Fortuitously the FTIR studies allowed monitoring of the formation of the products carbamic acid (CA) and carbamate salt (CS), as well as a key cyclized intermediate first discovered by Ikariya. These data allow additional insight into the mechanism as well as the central role which may be played by Au(I) carbamate formation as a higher energy resting state present in the catalytic cycle. The crystal structures of four of the new complexes and a detailed computational study relevant to the role of carbamic acid (CA) and carbamates in the catalytic cycle are also reported.
Keywords
N-HETEROCYCLIC CARBENE, CARBON-DIOXIDE, NHC-GOLD(I) COMPLEXES, AU-X, REACTIVITY, SILVER, NHC, HYDROPHENOXYLATION, ACID, ALKOXYLATION

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MLA
Al Chami Al Bayrakdar, Tahani, et al. “Dinuclear Gold(I) Complexes Bearing Alkyl-Bridged Bis(N-Heterocyclic Carbene) Ligands as Catalysts for Carboxylative Cyclization of Propargylamine : Synthesis, Structure, and Kinetic and Mechanistic Comparison to the Mononuclear Complex [Au(IPr)CI].” ORGANOMETALLICS, vol. 39, no. 15, 2020, pp. 2907–16, doi:10.1021/acs.organomet.0c00404.
APA
Al Chami Al Bayrakdar, T., Nahra, F., Davis, J. V., Gamage, M. M., Captain, B., Temprado, M., … Nolan, S. (2020). Dinuclear gold(I) complexes bearing alkyl-bridged bis(N-heterocyclic carbene) ligands as catalysts for carboxylative cyclization of propargylamine : synthesis, structure, and kinetic and mechanistic comparison to the mononuclear complex [Au(IPr)CI]. ORGANOMETALLICS, 39(15), 2907–2916. https://doi.org/10.1021/acs.organomet.0c00404
Chicago author-date
Al Chami Al Bayrakdar, Tahani, Fady Nahra, Jack V. Davis, Mohan M. Gamage, Burjor Captain, Manuel Temprado, Marco Marazzi, et al. 2020. “Dinuclear Gold(I) Complexes Bearing Alkyl-Bridged Bis(N-Heterocyclic Carbene) Ligands as Catalysts for Carboxylative Cyclization of Propargylamine : Synthesis, Structure, and Kinetic and Mechanistic Comparison to the Mononuclear Complex [Au(IPr)CI].” ORGANOMETALLICS 39 (15): 2907–16. https://doi.org/10.1021/acs.organomet.0c00404.
Chicago author-date (all authors)
Al Chami Al Bayrakdar, Tahani, Fady Nahra, Jack V. Davis, Mohan M. Gamage, Burjor Captain, Manuel Temprado, Marco Marazzi, Marina Saab, Kristof Van Hecke, Dominic Ormerod, Carl D. Hoff, and Steven Nolan. 2020. “Dinuclear Gold(I) Complexes Bearing Alkyl-Bridged Bis(N-Heterocyclic Carbene) Ligands as Catalysts for Carboxylative Cyclization of Propargylamine : Synthesis, Structure, and Kinetic and Mechanistic Comparison to the Mononuclear Complex [Au(IPr)CI].” ORGANOMETALLICS 39 (15): 2907–2916. doi:10.1021/acs.organomet.0c00404.
Vancouver
1.
Al Chami Al Bayrakdar T, Nahra F, Davis JV, Gamage MM, Captain B, Temprado M, et al. Dinuclear gold(I) complexes bearing alkyl-bridged bis(N-heterocyclic carbene) ligands as catalysts for carboxylative cyclization of propargylamine : synthesis, structure, and kinetic and mechanistic comparison to the mononuclear complex [Au(IPr)CI]. ORGANOMETALLICS. 2020;39(15):2907–16.
IEEE
[1]
T. Al Chami Al Bayrakdar et al., “Dinuclear gold(I) complexes bearing alkyl-bridged bis(N-heterocyclic carbene) ligands as catalysts for carboxylative cyclization of propargylamine : synthesis, structure, and kinetic and mechanistic comparison to the mononuclear complex [Au(IPr)CI],” ORGANOMETALLICS, vol. 39, no. 15, pp. 2907–2916, 2020.
@article{8694711,
  abstract     = {{Eight new dinuclear gold(I) complexes, [Au-2(L)X-2] (1-8), were synthesized using a straightforward synthetic procedure under very mild conditions. The complexes have been characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray structure analysis. Their catalytic activity was investigated in the carboxylative cyclization of propargylamine (PPA). A superior performance in comparison to [Au(IPr)Cl] (9) was obtained for complexes 1 and 2 having an eight-methylene bridge connecting two NHCs with an arene bearing an isopropyl substituent for X = Cl, Br. This prompted more detailed kinetic and mechanistic studies by FTIR comparing dinuclear complex 2 of X = Cl to complex 9. Fortuitously the FTIR studies allowed monitoring of the formation of the products carbamic acid (CA) and carbamate salt (CS), as well as a key cyclized intermediate first discovered by Ikariya. These data allow additional insight into the mechanism as well as the central role which may be played by Au(I) carbamate formation as a higher energy resting state present in the catalytic cycle. The crystal structures of four of the new complexes and a detailed computational study relevant to the role of carbamic acid (CA) and carbamates in the catalytic cycle are also reported.}},
  author       = {{Al Chami Al Bayrakdar, Tahani and Nahra, Fady and Davis, Jack V. and Gamage, Mohan M. and Captain, Burjor and Temprado, Manuel and Marazzi, Marco and Saab, Marina and Van Hecke, Kristof and Ormerod, Dominic and Hoff, Carl D. and Nolan, Steven}},
  issn         = {{0276-7333}},
  journal      = {{ORGANOMETALLICS}},
  keywords     = {{N-HETEROCYCLIC CARBENE,CARBON-DIOXIDE,NHC-GOLD(I) COMPLEXES,AU-X,REACTIVITY,SILVER,NHC,HYDROPHENOXYLATION,ACID,ALKOXYLATION}},
  language     = {{eng}},
  number       = {{15}},
  pages        = {{2907--2916}},
  title        = {{Dinuclear gold(I) complexes bearing alkyl-bridged bis(N-heterocyclic carbene) ligands as catalysts for carboxylative cyclization of propargylamine : synthesis, structure, and kinetic and mechanistic comparison to the mononuclear complex [Au(IPr)CI]}},
  url          = {{http://dx.doi.org/10.1021/acs.organomet.0c00404}},
  volume       = {{39}},
  year         = {{2020}},
}

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