TY - JOUR
T1 - Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation
AU - Bianchini, Claudio
AU - Brüggeller, Peter
AU - Claver, Carmen
AU - Czermak, Georg
AU - Dumfort, Alexander
AU - Meli, Andrea
AU - Oberhauser, Werner
AU - Suarez, Eduardo J.Garcia
PY - 2006
Y1 - 2006
N2 - The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ4, 4λ4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6) 2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc) 2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc) 2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The PdII complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol-1 with the diphosphine catalysts.
AB - The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ4, 4λ4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6) 2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc) 2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc) 2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The PdII complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol-1 with the diphosphine catalysts.
UR - https://www.scopus.com/pages/publications/33745021833
U2 - 10.1039/b601154c
DO - 10.1039/b601154c
M3 - Article
AN - SCOPUS:33745021833
SN - 1477-9226
SP - 2964
EP - 2973
JO - Dalton Transactions
JF - Dalton Transactions
IS - 24
ER -