609770-13-0Relevant articles and documents
Pyridine- and imidazole-phosphinimine bidentate ligand complexes: Considerations for ethylene oligomerization catalysts
Spencer, Liam P.,Altwer, Ramadan,Wei, Pingrong,Gelmini, Lucio,Gauld, James,Stephan, Douglas W.
, p. 3841 - 3854 (2003)
The series of 2-substituted diphenylphosphine pyridines 1-5 were synthesized and subsequently oxidized with silyl or aryl azides to give the series of pyridine-phosphinimine ligands 2-(Me3SiNPPh2)C5H4N (9), 2-(2,6-Me2C6H3NPPh2) C5H4N (10), 2-(2,6-i-Pr2C6 H3-NPPh2)C5 H4N (11), 2-(2,6-Me2C6H3 NPPh2)-6-MeC5H4N (12), 2-(2,6-i-Pr2C6H3NPPh2)-6- MeC5H4N (13), 2-(2,6-Me2C6H3NPPh2)-6- BnC5H4N (14), 2-(2,6-i-Pr2C6H3NPPh2)-6- BnC5H4N (15), 2-(2,6-Me2C6H3NPPh2)-6- SiMe3C5H4N (16), 2-(2,6-i-Pr2C6H3NPPh2)-6- SiMe3C5H4N (17), 2-(2,6-Me2C6H3NPPh2)-6- PhC5H4N (18), and 2-(2,6-i-Pr2C6H3NPPh2)-6- PhC5H4N (19). Attempts to oxidize the fluorinated phosphine 2-P(C6F5)2-6-PhC5 H3N (6) were unsuccessful. The ligand 9 reacted with PdCl2(PhCN)2 to the give the square-planar, diamagnetic compound (L)PdCl2 (20; L = 9), while the remaining ligands were used to prepare (L)NiBr2 and (L)-FeCl2; complexes 21-30 and 31-40 (L = 10-19), respectively. In these complexes the P atoms become part of the chelate backbone. In addition, the pyridine-phosphinimines 2-(Ph3P=NCH2)(C5H4N) (44), 2-(Ph3PNCH2)-6-Me(C5H3N) (45), and 2-(Ph3PNCH2)-6-Ph(C5H3N) (46) were also prepared from the reaction of 2-azidomethyl-pyridines with PPh3. In a similar fashion the complexes (L)PdCl2 (47, 48; L = 44, 45), (L)NiBr2 (49-51; L = 44-46), (L)FeCl2 (52, 53), and (L)CoCl2 (54, 55; L = 44, 45) were prepared. In addition, the imidazole-phosphines 1-Me-2-(PPh2)C3H2N2 (58), 1-Me-2-(PPh2)-4,5-Ph2C3N2 (59), and 1-Me-2-(PPh2)-C7H6N2 (60) were prepared and oxidized to give the imidazole-phosphinimines 1-Me-2-(2,6-Me2C6H3N=PPh2) C3H2N2 (61), 1-Me-2-(2,6-i-Pr2C6H3N=PPh2) C3H2N2 (62), 1-Me-2-(2,6-Me2C6H3N=PPh2)-4,5- Ph2C3N2 (63), 1-Me-2-(2,6-i-Pr2C6H3N=PPh2)-4,5- Ph2C3N2 (64), 1-Me-2-(2,6-Me2C6H3N=PPh2) C7H6N2 (65), 1-Me-2-(2,6-i-Pr2C6H3N=PPh2) C7H6N2 (66) and 1-Me-2-(2,6-i-Pr2C6H3N=PPh2)-4- (t-Bu)C3HN2 (67). Subsequent complexation afforded the species (L)PdCl2 (68; L = 61), (L)NiBr2 (69-75; L = 61-67), and (L)FeCl2 (76-82; L = 61-67). Preliminary screening for activity as catalyst precursors for ethylene polymerization indicated that ethylene oligomerization may be occurring. In the case of complexes 30, 40, 74, and 82 activation with Et2AlCl(ClC6H5) at 35°C under 300 psi of ethylene effected modest catalytic dimerization of ethylene to mainly C4 alkenes. DFT computations suggested that inclusion of P into the ligand results in diminished electrophilicity at the metal and thus a weakened ethylene-metal interaction, accounting for the modest catalytic activity. X-ray structure determinations were obtained for 2, 20, 26, 27, 35, 37, 40, 49-51, 54, 68, 79, and 82.
