§Institutes of Physical Science and Information
Technology, Anhui University, Hefei 230601, China
Abstract : The performance of a series of density functionals
has been tested for the insertions of ethylene, methyl acrylate (MA),
and vinyl bromide (VB) catalyzed by α-diimine palladium complexes.
Sixty-seven density functionals are screened, and the results are
compared with available experimental data. Eleven hybrid functionals
(M06, BHandH, mPW1PW91, HSEh1PBE, mPW3PBE, LC-ωPBE, mPW1PBE, PBE0,
M06-HF, M06-2X, M05-2X) showed better performance in the insertions of
both ethylene and MA, and could be therefore suitable for ethylene-MA
copolymerization. Meanwhile, three GGA (PW91PW91, HCTH, HCTH407), twometa -GGA (TPSSTPSS, tHCTH), and ten hybrid functionals (M06,
BHandH, TPSSh, B971, B98, B1B95, PBE0, M06-2X, tHCTHhyb, M05-2X) perform
well in ethylene-VB copolymerization. Besides, nine D3 or D3BJ augmented
functionals are found to be suitable for both copolymerization systems.
The D2 dispersion correction overestimated insertion energy barriers of
these monomers and is unsuitable for such copolymerization. In addition,
the double-zeta basis set is found to be sufficient for solvation
single-point calculation of these systems.
Keywords: Benchmark of DFT, Diimine palladium, Olefin
insertion, Polar monomer, Cross-coupling