期刊
CHEMICAL SCIENCE
卷 9, 期 1, 页码 143-151出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7sc03537c
关键词
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资金
- NSF [DMR-1308229]
- University of Chicago Materials Research Science and Engineering Center [DMR-1420709]
- National Natural Science Foundation of the P.R. China [21671162, 21471126]
- Materials Research Collaborative Access Team (MRCAT)
- Department of Energy
- DOE Office of Science [DE-AC02-06CH11357]
We report the synthesis of a terpyridine-based metal-organic layer (TPY-MOL) and its metalation with CoCl2 and FeBr2 to afford CoCl2.TPY-MOL and FeBr2.TPY-MOL, respectively. Upon activation with NaEt3BH, CoCl2 TPY-MOL catalyzed benzylic C-H borylation of methylarenes whereas FeBr2. TPY-MOL catalyzed intramolecular Csp(3)-H amination of alkyl azides to afford pyrrolidines and piperidines. X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy, UV-Vis-NIR spectroscopy, and electron paramagnetic spectroscopy (EPR) measurements as well as density functional theory (DFT) calculations identified M(THF)(2). TPY-MOL (M = Co or Fe) as the active catalyst with a M-II-(TPYc..)(2) electronic structure featuring divalent metals and TPY diradical dianions. We believe that site isolation stabilizes novel MII-(TPY..)(2) (M = Co or Fe) species in the MOLs to endow them with unique and enhanced catalytic activities for C-sp(3)-H borylation and intramolecular amination over their homogeneous counterparts. The MOL catalysts are also superior to their metal-organic framework analogs owing to the removal of diffusion barriers. Our work highlights the potential of MOLs as a novel 2D molecular material platform for designing single-site solid catalysts without diffusional constraints.
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