Palladacyclic compounds [Pd(C6H4(C6H5C=O)C=N R)(N N)] [X] (R=Et, iPr, 2,6-iPr2C6H3;N N=bpy=2,2’-bipyridine, or 1,4-(o,o’-dialkylaryl)-1,4-diazabuta-1,3-dienes; [X] =[BF4] or [PF6] )were synthesized from the dimers [{Pd(C6H4(C6H5C=O)C=N R)(m-Cl)} 2] and N N ligands. Their interionic structure in CD2Cl2 was determined by means of 19F, 1H-HOESY experiments and compared with that in the solid state derived from X-ray single-crystal studies. [Pd(C6H4(C6H5C=O)C=N R)(N N)] [X] complexes were found to copolymerize CO and p-methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4-(o,o’-dimethylaryl)-1,4-diazabuta-1,3-dienes were used, respectively. The reactions with CO and p-methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd C bonds were isolated and completely characterized in solution.
C. ZUCCACCIA, G. BELLACHIOMA, G. CARDACI, A. MACCHIONI, B. BINOTTI, CARFAGNA C (2006). Synthesis, interionic structure, and reactivity toward CO and p-methylstyrene of palladacyclic compounds bearing a -diimine ligands. HELVETICA CHIMICA ACTA, 89(8), 1524-1546 [10.1002/hlca.200690155].
Synthesis, interionic structure, and reactivity toward CO and p-methylstyrene of palladacyclic compounds bearing a -diimine ligands
CARFAGNA, CARLA
2006
Abstract
Palladacyclic compounds [Pd(C6H4(C6H5C=O)C=N R)(N N)] [X] (R=Et, iPr, 2,6-iPr2C6H3;N N=bpy=2,2’-bipyridine, or 1,4-(o,o’-dialkylaryl)-1,4-diazabuta-1,3-dienes; [X] =[BF4] or [PF6] )were synthesized from the dimers [{Pd(C6H4(C6H5C=O)C=N R)(m-Cl)} 2] and N N ligands. Their interionic structure in CD2Cl2 was determined by means of 19F, 1H-HOESY experiments and compared with that in the solid state derived from X-ray single-crystal studies. [Pd(C6H4(C6H5C=O)C=N R)(N N)] [X] complexes were found to copolymerize CO and p-methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4-(o,o’-dimethylaryl)-1,4-diazabuta-1,3-dienes were used, respectively. The reactions with CO and p-methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd C bonds were isolated and completely characterized in solution.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.