Olefin Hydroarylation Catalyzed by (Pyridyl-Indolate)Pt(II) Complexes: Catalytic Efficiencies and Mechanistic Aspects
Creators
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1.
University of California, Berkeley
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2.
Lawrence Berkeley National Laboratory
Abstract
A series of Pt(II) complexes of the type (N–N)PtPh(SR_2) (N–N = 2,2′-pyridyl-indolate) were prepared, and their performance as catalysts for the hydroarylation of olefins was assessed. Evidence that the catalysis is homogeneous and is Pt-mediated is provided by control experiments with added hindered base (2,6-di-tert-butyl-4-methylpyridine) and Hg(0). Two potential catalytic intermediates, (^tBuPyInd)PtPh(C_2H_4) and (^tBuPyInd)Pt(CH_2CH_2Ph)(C_2H_4), were synthesized, and their catalytic efficacy was explored. Additionally, decomposition and deactivation pathways, including styrene formation via β-hydride elimination and ligand reductive demetalation, were identified.
Additional Information
© 2017 American Chemical Society. Received: May 12, 2017; Published: May 18, 2017. This work was primarily funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Contract No. DE-AC02-05CH11231. We acknowledge the NIH (Grant Nos. SRR023679A and 1S10RR016634-01) and NSF (Grant No. CHE-0130862) for funding of the College of Chemistry NMR facility (University of California, Berkeley). The Central California 900 MHz NMR Facility (University of California, Berkeley) is acknowledged for providing access to the 900 MHz NMR spectrometer and is supported by the NIH (GM68933). The QB3/Chemistry Mass Spectrometry Facility (University of California, Berkeley) is acknowledged for help and access to the LTQ-FT ESI-HRMS (SN 06053F) and AutoSpec EI-HRMS (SN P749, property ID# 20081000740) instruments. We also acknowledge the NIH (Grant No. S10-RR027172) for funding of the ChexRay X-ray crystallographic facility (College of Chemistry, University of California, Berkeley). B.A.S. acknowledges the NSF-GRFP for a fellowship (DGE 1106400). We thank Dr. Michael I. Lipschutz for X-ray structure determinations of 2a–c, 3, and 4. Dr. Jeffery G. Pelton and Dr. Hasan Celik are thanked for help with high-field NMR spectroscopy experiments. Dr. Jeffery C. Holder is thanked for help with quantitative GC analysis. Professor Robert G. Bergman, Dr. Nicholas A. Phillips, Dr. Daniel S. Levine, Patrick W. Smith, and Micah S. Ziegler are thanked for providing useful discussions and insights.Attached Files
Supplemental Material - cs7b01560_si_001.pdf
Supplemental Material - cs7b01560_si_002.cif
Supplemental Material - cs7b01560_si_003.cif
Supplemental Material - cs7b01560_si_004.cif
Supplemental Material - cs7b01560_si_005.cif
Supplemental Material - cs7b01560_si_006.cif
Files
cs7b01560_si_001.pdf
Files
(4.5 MB)
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Additional details
Identifiers
- Eprint ID
- 77604
- DOI
- 10.1021/acscatal.7b01560
- Resolver ID
- CaltechAUTHORS:20170519-131615970
Funding
- Department of Energy (DOE)
- DE-AC02-05CH11231
- NIH
- SRR023679A
- NIH
- 1S10RR016634-01
- NSF
- CHE-0130862
- NIH
- GM68933
- NIH
- S10‐RR027172
- NSF Graduate Research Fellowship
- DGE-1106400
Dates
- Created
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2017-05-19Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field