Synthesis and Characterization of Proximal Dinuclear Complexes of Palladium Supported by 2,6-Bis(arylimino)phenoxy (aryl = 2,6-diisopropylphenyl and 2,4,6-tri-tert-butylphenyl) and 3,6-Bis(imin

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• 作者：Kouji Ohno ; Kenji Arima ; Shinji Tanaka ; Tsuneaki Yamagata ; Hayato Tsurugi ; Kazushi Mashima
• 刊名：Organometallics
• 出版年：2009
• 出版时间：June 8, 2009
• 年：2009
• 卷：28
• 期：11
• 页码：3256-3263
• 全文大小：215K
• 年卷期：v.28,no.11(June 8, 2009)
• ISSN：1520-6041

文摘

Two kinds of binucleating ligands, 2,6-bis(arylimino)phenoxy (1a: aryl = 2,6-diisopropylphenyl; 1b: aryl = 2,4,6-tri-tert-butylphenyl) and 3,6-bis(imino(2,6-diisopropylphenyl))pyridazine (2), were prepared, and their proximal complexation with two palladium atoms was studied. Treatment of the sodium compounds of 1a,b with 2 equiv of PdCl₂(PhCN)₂ and PdMeCl(cod) afforded the corresponding homobimetallic complexes, [2,6-bis(arylimino)phenoxy][RPd(μ-Cl)PdR] (4a: R = Cl, aryl = 2,6-diisopropylphenyl; 4b: R = Cl, aryl = 2,4,6-tri-tert-butylphenyl; 7a: R = Me, aryl = 2,6-diisopropylphenyl; 7b: R = Me, aryl = 2,4,6-tri-tert-butylphenyl), whose structures were characterized spectroscopically and crystallographically. In the reaction between the sodium compound of 1a with 1 equiv of PdCl₂(PhCN)₂, we detected the NaCl adduct of mononuclear palladium species 5a, which, upon release of NaCl, formed a dimeric complex, ([2,6-bis(2,6-diisopropylphenylimino)phenoxy](PdCl])₂ (4a), as confirmed by X-ray analysis. Complexation of 2 with 2 equiv of PdCl₂(PhCN)₂ and PdMeCl(cod) in the presence of 1 equiv of AgBF₄ resulted in the formation of the corresponding cationic complexes ([3,6-bis(imino(2,6-diisopropylphenyl))pyridazine][RPd(μ-Cl)PdR])(BF₄) (9a: R = Cl; 9b: R = Me), whose RPd(μ-Cl)PdR skeletons (R = Cl and Me) were revealed spectroscopically and crystallographically.