Functionalized Palladacycles with Crown Ether Rings Derived from Terdentate [C,N,N] Ligands. Crystal and Molecular Structure of the Dinuclear Palladium/Silver Complex [Pd{3,4-(AgC

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• 作者：Digna Va虂zquez-Garci虂a ; Alberto Ferna虂ndez ; Margarita Lo虂pez-Torres ; Antonio Rodri虂guez ; Alexis Varela ; M. Teresa Pereira ; Jose虂 M. Vila ; Jesu虂s J. Ferna虂ndez
• 刊名：Organometallics
• 出版年：2011
• 出版时间：February 14, 2011
• 年：2011
• 卷：30
• 期：3
• 页码：396-404
• 全文大小：957K
• 年卷期：v.30,no.3(February 14, 2011)
• ISSN：1520-6041

文摘

Reaction of 3,4-(C₁₀H₂₀O₆)C₆H₃C(Me)鈺怤N(H)[3鈥?(CF₃)C₄H₂N₂] (a) and 3,4-(C₁₀H₂₀O₆)C₆H₃C(Me)鈺怤N(H)(4鈥?ClC₄H₂N₂) (b) with Li₂[PdCl₄] and sodium acetate in methanol at room temperature yielded the mononuclear cyclometalated complexes [Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)[3鈥?(CF₃)C₄H₂N₂]}(Cl)] (1a) and Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)(4鈥?ClC₄H₂N₂)}(Cl)] (1b), respectively, with the ligand as terdentate [C,N,N]. The reaction of 1a and 1b with silver trifluoromethanesulfonate and triphenylphosphine yielded [Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)[3鈥?(CF₃)C₄H₂N₂]}(PPh₃)][CF₃SO₃] (2a) and [Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)(4鈥?ClC₄H₂N₂)}(PPh₃)][CF₃SO₃] (2b) with the phosphine ligand occupying the vacant coordination position after chlorine abstraction; these were deprotonated at the hydrazine nitrogen after treatment with sodium acetate, yielding the [Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N[3鈥?(CF₃)C₄H₂N₂]}(PPh₃)] (3a) and [Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(4鈥?ClC₄H₂N₂)}(PPh₃)] (3b). Further treatment of 2b with silver trifluoromethanesulfonate gave 5b. Reaction of 2a and 2b with a Ag(I) salt and the tertiary diphosphine Ph₂P(CH₂)₄PPh₂ (dppb) in 2:1 molar ratio gave the dinuclear complexes [{Pd{3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)[3鈥?(CF₃)C₄H₂N₂]}}₂(渭-PPh₂(CH₂)₄PPh₂)][CF₃SO₃]₂ (4a) and [{Pd[3,4-(C₁₀H₂₀O₆)C₆H₂C(Me)鈺怤N(H)(4鈥?ClC₄H₂N₂)]}₂((渭-PPh₂(CH₂)₄P-Ph₂)][CF₃SO₃]₂ (4b) with the diphosphine as a bridging ligand. The crystal structures of complexes 1a and 5b are described, the latter crystallized with a Ag(I) atom complexed to the crown ether ring putting forward the ability of the complex to act as a metaloligand.