TY - JOUR
T1 - Effect of phosphine and phosphine sulfide ligands on the cobalt-catalyzed reductive coupling of 2-iodobutane with n-butyl acrylate
AU - Aizawa, Sen Ichi
AU - Fukumoto, Koichi
AU - Kawamoto, Tatsuya
N1 - Funding Information:
This research was supported by Grant-in-Aid for Scientific Research (No. 23550068) from the Japan Society for the Promotion of Science.
PY - 2013
Y1 - 2013
N2 - Tris[2-(diphenylphosphino)ethyl]phosphine disulfide (pp3S2), in which two terminal phosphino groups are selectively sulfidated, was prepared by utilizing the selective sulfidation reaction of [PdI(pp3)]I. Co(II) complexes with bidentate, tridentate and tetradentate phosphines and pp3S2 were prepared from anhydrous CoI2. X-ray crystal analyses revealed that the reaction of CoI2 with 1 equivalent of 1,2-bis(diphen-ylphosphino) ethane (p2) gave rise to partial oxidation of p2 to give the dicationic octahedral [Co(p2O2)2(CH 3CN)2]2+ (p2O2 = p 2 dioxide) and dianionic p2O-bridged tetrahedral dinuclear [CoI3(p2-O)CoI3]2 (p2O = p2 monooxide) complexes, while the reaction with 2 equivalents of p2 gave the square-pyramidal [CoI(p2)2] + complex. The catalytic activity for the Co-catalyzed coupling reaction of 2-iodobutane with n-butyl acrylate was compared using multidentate phosphines and phosphine sulfides as ligands, and the efficiency of the phosphine sulfides was shown. The tendency for multidentate phosphine to deactivate the Co-catalysis can substantiate an oxidative addition driven mechanism in which the multidentate ligand should interfere with the formation of the alkyl halide Co(III) adduct and subsequent coordination of an alkene.
AB - Tris[2-(diphenylphosphino)ethyl]phosphine disulfide (pp3S2), in which two terminal phosphino groups are selectively sulfidated, was prepared by utilizing the selective sulfidation reaction of [PdI(pp3)]I. Co(II) complexes with bidentate, tridentate and tetradentate phosphines and pp3S2 were prepared from anhydrous CoI2. X-ray crystal analyses revealed that the reaction of CoI2 with 1 equivalent of 1,2-bis(diphen-ylphosphino) ethane (p2) gave rise to partial oxidation of p2 to give the dicationic octahedral [Co(p2O2)2(CH 3CN)2]2+ (p2O2 = p 2 dioxide) and dianionic p2O-bridged tetrahedral dinuclear [CoI3(p2-O)CoI3]2 (p2O = p2 monooxide) complexes, while the reaction with 2 equivalents of p2 gave the square-pyramidal [CoI(p2)2] + complex. The catalytic activity for the Co-catalyzed coupling reaction of 2-iodobutane with n-butyl acrylate was compared using multidentate phosphines and phosphine sulfides as ligands, and the efficiency of the phosphine sulfides was shown. The tendency for multidentate phosphine to deactivate the Co-catalysis can substantiate an oxidative addition driven mechanism in which the multidentate ligand should interfere with the formation of the alkyl halide Co(III) adduct and subsequent coordination of an alkene.
KW - Activated alkene
KW - Cobalt-catalyzed reductive coupling
KW - Oxidative addition driven mechanism
KW - Phosphine sulfide ligand
UR - http://www.scopus.com/inward/record.url?scp=84885169601&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2013.06.013
DO - 10.1016/j.poly.2013.06.013
M3 - 学術論文
AN - SCOPUS:84885169601
SN - 0277-5387
VL - 62
SP - 37
EP - 41
JO - Polyhedron
JF - Polyhedron
ER -