C(sp3)−H bond activation by vinylidene gold(I) complexes: a concerted asynchronous or stepwise process?
A detailed analysis of the C(sp3)−H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C−C bond formation, and (iii) σ to π rearrangement of the lone pa...
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article (Journal) |
| Language: | English |
| Published: |
2017
|
| In: |
Chemistry - a European journal
Year: 2017, Volume: 23, Issue: 63, Pages: 16097-16103 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201703815 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1002/chem.201703815 Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201703815 
|
| Author Notes: | Johannes E.M.N. Klein, Gerald Knizia, Laura Nunes dos Santos Comprido, Johannes Kästner and A. Stephen K. Hashmi |
| Summary: | A detailed analysis of the C(sp3)−H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C−C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C-H-C three-centre two-electron (3c-2e) bond. The role of π-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies. |
|---|---|
| Item Description: | Version of record online: October 19, 2017 Gesehen am 28.06.2018 Im Titel ist die Zahl 3 als Hochzahl dargestellt |
| Physical Description: | Online Resource |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.201703815 |