Amido-Pincer-Nickel-Catalyzed Activation And Transformation Of C-Cl, C-F And C-N Bonds

Chapter1describes synthesis and characterization of a series of P,N,N-pincer nickel and palladium complexes. P,N,N-Pincer nickel complexes [Ni（Cl）{N（2-R2P-C6H4）（2’-Me2NC6H4）}]（R=Ph, la; R=i-Pr,1b; R=Cy, lc） and palladium complex [Pd（Cl）{N（2-Ph₂PC₆H₄）（2’-Me₂NC₆H₄）}]（2a） were synthesized. These complexes were characterized by¹H,¹³C and³¹PNMR spectroscopy and elemental analyses. The structure of complex la was also confirmed by single crystal X-ray diffraction techniques.Chapter2is about the cross-coupling of aryl fluorides with aryl Grignard reagents catalyzed by the P,N,N-pincer nickel complexes. The catalytic activity order of the complexes for the cross-coupling is approximately la>1b≈1c. Complex la effectively catalyzes the cross-coupling of （hetero）aryl fluorides with aryl Grignard reagents in toluene at room temperature.Chapter3presents the cross-coupling of aryl chlorides with arylzinc reagents catalyzed by complex la. Complex la can drive the reaction to proceed smoothly in a2:1mixture of THF and NMP at80℃with low catalyst loadings, good functional group compatibility and wide scope of substrates.Chapter4presents the cross-coupling of aryltrimethylammonium salts with arylzinc reagents catalyzed by the P,N,N-pincer nickel complexes. Complex la catalyzes the reaction with low catalyst loadings. Nitrogen-containing heterocycles and functional groups such as PhC（O）, COOEt, C（O）NEt2and CF3are tolerated.