The First Complexes with Two Metallacycles Fused Around a Common Aryl Substituent: 鈥淎kimbo鈥?Complexes

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• 作者：Mar铆a-Teresa Chicote ; Inmaculada Vicente-Hern谩ndez ; Peter G. Jones ; Jos茅 Vicente
• 刊名：Organometallics
• 出版年：2012
• 出版时间：September 10, 2012
• 年：2012
• 卷：31
• 期：17
• 页码：6252-6261
• 全文大小：416K
• 年卷期：v.31,no.17(September 10, 2012)
• ISSN：1520-6041

文摘

Following the reaction sequence i) oxidative addition of RNHC(O)C₆H₃I₂-2,6 (R = Me, Tol) to [Pd₂(dba)₃]路dba in the presence of chelating ligands NN or XyNC (Xy = C₆H₃Me₂-2,6), ii) treatment of the resulting complexes with TlTfO or Tl(acac) (acac = acetylacetonato), and iii) insertion of unsaturated molecules (CO, XyNC, MeO₂CC鈮CO₂Me, MeC(O)CH鈺怌H₂) into one of the Pd鈥揅_aryl bonds of the resulting complexes allowed the synthesis of aryldipalladated complexes containing the ligands L1 = 渭-C,C-{C₆H₃C(O)NHR}-2,6, L2 = 渭-C,C-{C₆H₃C(O)NHMe}(C鈺怤Xy)₂-2,6, L3 = 渭-C,O,C-{C₆H₃C(O)NHMe}-2,6, L4 = 渭-C,O,C,N-{C₆H₃C(O)NR}-2,6, L6 = 渭-C,N,C,O-{C₆H₃C(O)NR}-2-(C鈺怬)-6, L7 = 渭-C,N,C,O-{C₆H₃C(O)NR}-2-{C(CO₂Me)鈺怌(CO₂Me)}-6, L8 = 渭-C,N,C,O-{C₆H₃C(O)NR}-2-(C鈺怤Xy)-6 and two arylmonopalladated complexes with the ligands L5 = C,O-{C₆H₄C(O)NHMe}-2 and L9 = C,N-{C₆H₃C(O)NTol}-2-{CH鈺怌HC(O)Me}-6. The complex with the ligand L7 inserted CO into the second Pd鈥揅_aryl bond to give an L10-Pd₂ complex (L10 = 渭-C,N,C,O-{C₆H₃C(O)NTol}(C鈺怬)-2-{C(CO₂Me)鈺怌(CO₂Me)}-6. The dipalladated species display a different environment for each palladium atom and represent the first systems containing two 5 + 5, 5 + 6, 5 + 7, or 6 + 7-membered palladacycles condensed over the central benzamide group. The two arms of the ligands L4 and L6-L8 and L10 are 鈥渁kimbo鈥? and we coin this name both for the ligands and for the dimetallic complexes bearing them. The crystal structure of a [{Pd(NN)}₂L6]⁺ complex has been determined.