Metal-organic layers stabilize earth-abundant metal-terpyridine diradical complexes for catalytic C-H activation.

Autor: Lin Z; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Thacker NC; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Sawano T; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Drake T; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Ji P; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Lan G; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu., Cao L; Collaborative Innovation Center of Chemistry for Energy Materials , State Key Laboratory of Physical Chemistry of Solid Surfaces , Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , PR China., Liu S; Research Computing Center , University of North Carolina , Chapel Hill , North Carolina 27599-3420 , USA., Wang C; Collaborative Innovation Center of Chemistry for Energy Materials , State Key Laboratory of Physical Chemistry of Solid Surfaces , Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , PR China., Lin W; Department of Chemistry , University of Chicago , 929 E. 57th St. , Chicago , Illinois 60637 , USA . Email: wenbinlin@uchicago.edu.; Collaborative Innovation Center of Chemistry for Energy Materials , State Key Laboratory of Physical Chemistry of Solid Surfaces , Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , PR China.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2017 Oct 30; Vol. 9 (1), pp. 143-151. Date of Electronic Publication: 2017 Oct 30 (Print Publication: 2018).
DOI: 10.1039/c7sc03537c
Abstrakt: We report the synthesis of a terpyridine-based metal-organic layer (TPY-MOL) and its metalation with CoCl 2 and FeBr 2 to afford CoCl 2 ·TPY-MOL and FeBr 2 ·TPY-MOL, respectively. Upon activation with NaEt 3 BH, CoCl 2 ·TPY-MOL catalyzed benzylic C-H borylation of methylarenes whereas FeBr 2 ·TPY-MOL catalyzed intramolecular C sp 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 -(TPY˙˙) 2- electronic structure featuring divalent metals and TPY diradical dianions. We believe that site isolation stabilizes novel M II -(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.
Databáze: MEDLINE
Externí odkaz: