Organometallics p. 1087 - 1101 (2001)
Update date:2022-07-30
Topics:
Yagyu, Takeyoshi
Hamada, Makiko
Osakada, Kohtaro
Yamamoto, Takakazu
Iodo(aryl)palladium complexes, [PdI{C6H3 (CF3)2-3,5}(N-N)] (N-N = tmeda, bpy, 4,4′-dimethyl-2,2′-bipyridine (Me2bpy)), react with AgBF4 in CH3CN, acetone, and THF to yield stable cationic arylpalladium complexes [Pd{C6H3 (CF3)2-3,5}(N-N)(solv)]BF4. A similar reaction of AgBF4 with [PdI(C6H3Me2-3,5) (bpy)] in CH3CN gives [Pd(C6H3Me2- 3,5)(bpy)(CH3CN)]BF4. The complex does not change its NMR spectrum for 1 h at room temperature in CD3CN but undergoes decomposition upon dissolution in acetone to release 3,3′,5,5′- tetramethylbiphenyl. Addition of AgBF4 to acetone or THF solutions of [PdI(Ar)(bpy)] (Ar = Ph, C6H3Me2-3,5) and of [PdI(Ar)(Me2bpy)] (Ar = C6H4OMe-4, C6H3Me2-3,5) does not lead to isolation of the cationic arylpalladium complexes and causes intermolecular coupling of the aryl ligands to yield the corresponding biaryls. The reaction of AgBF4 with [PdI(C6H3Me2-3,5)(bpy)] in the presence of an excess amount of dimethyl acetylenedicarboxylate (DMAD) in CH3CN gives [Pd(CZ=CZ-CZ=CZ-C6H3Me2-3,5)(bpy) (CH3CN)]BF4 (Z = COOMe) via insertion of two acetylene molecules into the Pd-aryl bond. A similar reaction in acetone or THF causes insertion of three DMAD molecules into the Pd-aryl bond and cyclization of the formed Pd-(CZ=CZ)3-Ar group to give the product containing a cyclopentadiene structure in the ligand. [PdI(CZ=CZ-C6H3 Me2-3,5)(bpy)] reacts with AgBF4 in CH3CN to form a cationic complex, [Pd(CZ=CZ-C6H3Me2-3,5) (bpy)(CH3CN)]BF4. A series of cationic Pd complexes, formed through insertion of one, two, and three alkyne molecules into the Pd-aryl bond, are characterized by X-ray crystallography or NMR spectroscopy. Phenylallene reacts with [PdI(C6H3Me2-3,5) (bpy)] in the presence of AgBF4 to give [Pd{η3-CH2C-(C6H3 Me2-3,5)CHPh}(bpy)]BF4 via insertion of the C=C double bond of the allene into the Pd-C bond of the cationic arylpalladium complex. The π-allylpalladium complex crystallizes exclusively in a form with a syn-oriented phenyl substituent but exists in solution as a mixture of the isomers with a syn or anti phenyl substituent.
View MoreChiral Quest (Suzhou) Company Ltd
website:http://www.chiralquest.com
Contact:+86-0512-62956066
Address:B1/9, 218 Xinghu Street, Suzhou Industrial Park
Onlychem (Jinan)Biotech Co.,Ltd
Contact:86-531-83175885
Address:No. 44, Honglou South Road, Jinan,China
Guangzhou Chemical Reagent Factory
Contact:+86-20-8435 9820 or 8435 7345
Address:Southern Guangzhou, Guangdong, China
Laohekou Jinghong Chemical Co.,Ltd
Contact:+86-0710-3702747
Address:163.East,Huagong Road,Laohekou
Shangyu Sanhechemicals Co.,LTD.
Contact:86-0571-56696839
Address:Num.2952,Nanhuan Road,Binjiang District,Hangzhou,China
Doi:10.1021/ja0126226
(2002)Doi:10.1039/j39710002756
(1971)Doi:10.1039/c7ob02834b
(2018)Doi:10.1021/om000649c
(2001)Doi:10.1039/c6ra03798d
(2016)Doi:10.1016/S0040-4039(03)01206-1
(2003)