期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 121, 期 40, 页码 7709-7716出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.7b06856
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- Euskal Herriko Unibertsitatea (Univ. of the Basque Country)
- Gipuzkoako Foru Aldundia (Provincial Government of Guipuzkoa)
- Eusko Jaurlaritza (Basque Government)
Palladium phosphine sulfonate complexes constitute an efficient family of catalysts for both homo-polymerization of ethylene and copolymerization of ethylene with a number of polar monomers. Their catalytic mechanisms have been extensively studied but not fully understood at the electronic structure level. The energy decomposition analysis, complemented with the inspection of the natural orbitals for chemical valence, reveals that their catalytic activity can be rationalized in terms of the so-called trans effect. Furthermore, our analysis shows that the competition for the sigma donation of the two ligands PMe3 and L, of the palladium phosphine sulfonate complexes, to the same orbital of Pd in the trans isomer and to different orbitals in the cis isomer is the origin of the trans effect. Although the dominance of the phosphine group prevents an efficient interaction of the ligand L with the Pd atom, the large stabilization gained by the phosphine group renders a very stable trans complex.
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