Page 7 of 9
Green Chemistry
DOI: 10.1039/C8GC00754C
Journal Name
ARTICLE
In a typical experiment, PdCl2(MeCN)2 (0.05 mmol), L1 (0.05 Intensity data were collected at 296(2) K on a Bruker
mmol) (or the other ligand) were mixed with phenylacetylene (5 SMARTAPEX II diffractometer using graphite monochromated
mmol, or the other alkyne) and methanol (3 mL, or the other Mo-Kα radiation (λ = 0.71073 Å). Data reduction included
alcohol). The mixture was added in a 50 mL sealed Teflon-lined absorption corrections by the multi-scan method (Table S1).
stainless steel autoclave which was purged with CO (0.3 MPa) for The structures were solved by direct methods and refined by
two times and then pressured by CO to 1.0 MPa. Then the reaction full matrix least-squares using SHELXS-97 (Sheldrick, 1990),
mixture was stirred vigorously at appointed temperature for some with all non-hydrogen atoms refined anisotropically. Hydrogen
time. Upon completion, the autoclave was cooled down to room atoms were added at their geometrically ideal positions and
temperature and slowly depressurized. The solution was analyzed refined isotropically.
by GC to determine the conversions (n-dodecane as internal
standard) and the selectivities (normalization method), and the
products were further identified by GC-mass spectrometry, 1H NMR
and 13C NMR.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21673077 and 21473058).
We acknowledge the support of the NYU-ECNU Center for
Computational Chemistry at NYU Shanghai. We also thank the
supercomputer center of ECNU for providing computer time.
When [Bmim]NTf2 was used as the solvent for the tandem bis-
methoxycarbonylation, in which phenylacetylene (5 mmol), MeOH
(3 mL), PdCl2(MeCN)2 (0.05 mmol), and L1 (0.1 mmol) were mixed
sequentially. Upon reaction, the IL phase was washed with n-
hexane (3 mL × 3) to completely extract the reactants and products
out of the IL phase. The combined organic phase was analyzed by
GC and ICP-OES. The remaining IL phase was directly used without
further treatment for the next run (if required MeOH was added
additionally).
Notes and references
‡ CCDC 1573652 contains the supplementary crystallographic
data in this paper. These data can be obtained free of charge
from the Cambridge Crystallographic Data Centre via
Computational methods
The DFT calculation was carried out using the Gaussian 09 software
package.34 The structural optimization of F was performed using the
M06 functional35,36combined with the Lanl2dz37,38 and 6-
31G*39basis set, denoted as the M06/Lanl2dz+6-31G*method. The
Lanl2dz basis set combined with the relativistic effective core
potential37,38 was used to describe the metal element Pd and the 6-
31G* basis set was utilized to describe the nonmetallic elements C,
O, P and H. The solvent effect of methanol was evaluated using the
SMD40 model at the same computational level, with the dielectric
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