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Article Abstract
The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC-based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E- and gem-enyne formation through a common reaction sequence involving hydrometallation and rate-determining C-C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head-to-head coupling, contrasting the high selectivity for head-to-tail coupling observed for the corresponding acyclic pincer ligand.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6175324 | PMC |
| http://dx.doi.org/10.1002/anie.201807028 | DOI Listing |
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