Synthesis and reactions of heterodinuclear organopalladium complex having an unsymmetrical PN ligand

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• 作者：Nobuyuki Komine ; Susumu Tsutsuminai ; Masafumi Hirano ; Sanshiro Komiya
• 关键词：Heterodunuclear organopalladium complex ; Unsymmetrical PN ligand ; CO insertion
• 刊名：Journal of Organometallic Chemistry
• 出版年：2007
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：1 October 2007
• 卷：692
• 期：21
• 页码：4486-4494
• 文件大小：560 K

摘要

Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et₂NC₂H₄PPh₂-κ²N,P)RPd–ML_n (ML_n = Co(CO)₄; R = Me (2a), Ph (2b), ML_n = MoCp(CO)₃; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et₂NC₂H₄PPh₂-κ²N,P) (X = I, NO₃) with Na⁺[ML_n]⁻. Reversible dissociation of the Pd–N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et₂NC₂H₄PPh₂-κ²N,P)(RCO)Pd–Co(CO)₄ (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et₂NC₂H₄PPh₂-κ²N,P) (1a), and methylpalladium–cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-κ²P,P′)MePd–Co(CO)₄ (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N′,N′-tetramethylethylenediamine ligand.