Journal
CHEMICAL SCIENCE
Volume 6, Issue 11, Pages 6572-6582Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc02161h
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Funding
- US National Science Foundation [CHE-1310007]
- Welch Foundation [A-1717]
- Fundamental Research Funds for the Central Universities of China [AUGA5710013115]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1300299] Funding Source: National Science Foundation
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Following the report on the successful use of SiNN pincer complexes of iridium as catalysts for dehydrogenative borylation of terminal alkynes (DHBTA) to alkynylboronates, this work examined a wide variety of related pincer ligands in the supporting role in DHBTA. The ligand selection included both new and previously reported ligands and was developed to explore systematic changes to the SiNN framework (the 8-(2-diisopropylsilylphenyl)aminoquinoline). Surprisingly, only the diarylamido/bis(phosphine) PNP system showed any DHBTA reactivity. The specific PNP ligand (bearing two diisopropylphosphino side donors) used in the screen showed DHBTA activity inferior to SiNN. However, taking advantage of the ligand optimization opportunities presented by the PNP system via the changes in the substitution at phosphorus led to the discovery of a catalyst whose activity, longevity, and scope far exceeded that of the original SiNN archetype. Several Ir complexes were prepared in a model PNP system and evaluated as potential intermediates in the catalytic cycle. Among them, the (PNP) Ir diboryl complex and the borylvinylidene complex were shown to be less competent in catalysis and thus likely not part of the catalytic cycle.
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