Structural studies of PdCl2L2 complexes with fluorinated phosphines, phosphites, and phosphinites as precursors of benzyl bromide carbonylation catalysts, and and X-ray crystal structure of cis-PdCl2[PPh2(OEt)]2
| Autor: | Hubert Bartosz-Bechowski, Zbigniew Ciunik, Katarzyna Niesyty, Anna M. Trzeciak, Józef J. Ziółkowski |
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| Rok vydání: | 2001 |
| Předmět: | |
| Zdroj: | Canadian Journal of Chemistry. 79:752-759 |
| ISSN: | 1480-3291 0008-4042 |
| DOI: | 10.1139/v01-075 |
| Popis: | PdCl2L2-type complexes with phosphines (L = PPhx(C6F5)3-x (x = 0-3)), phosphites (L = P(OMe)3, P(OPh)3, P(OEt)3), and phosphinites (L = PPh2(OC6F5), PPh2(O-3,5-F2C6H3), PPh2(OEt), PPh2(O-n-Bu), PPh2(O-t-Bu)) were synthesized and characterized by UV-vis and 31P NMR methods. PdCl2L2 complexes with less sterically demanding phosphines (Θ < 140°) exist as cis isomers, which is confirmed by the X-ray structure of cis-PdCl2[PPh2(OEt)]2. These complexes react with CO in the presence of NEt3 forming Pd(CO)xLy (x + y = 4) type carbonyls characterized by IR spectra. All PdCl2L2 complexes studied are active as precursors of benzyl bromide carbonylation catalysts at 40°C and 1 atm CO; however, the activity of the cis isomers is higher than that of the trans isomers. The highest yields of the carbonylation product, phenylacetic acid methyl ester, were obtained using cis-PdCl2[P(OMe)3]2 (92%), cis-PdCl2[P(OPh)3]2 (89%), and cis-PdCl2[PPh2(O-n-Bu)]2 (78%) as catalyst precursors.Key words: palladium complexes, fluorinated phosphines, benzyl bromide carbonylation. |
| Databáze: | OpenAIRE |
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