Novel Bidentate [N,S] Palladacycle Metalloligands. 1H鈥?sup>15N HMBC as a Decisive NMR Technique for the Structural Characterization of Palladium鈥揜hodium and Palladium鈥揚a

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• 作者：M. Teresa Pereira ; Jos茅 M. Antelo ; Luis A. Adrio ; Javier Mart铆nez ; Juan M. Ortigueira ; Margarita L贸pez-Torres ; Jos茅 M. Vila
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 14, 2014
• 年：2014
• 卷：33
• 期：13
• 页码：3265-3274
• 全文大小：558K
• ISSN：1520-6041

文摘

Treatment of tetranuclear palladacycles with 2-(diphenylphosphino)pyridine, Ph₂Ppy, in acetone at room temperature for 10 h, gave the new bidentate [N,S] palladacycle metalloligands 1鈥?b>7. Treatment of [Rh₂Cl₂(CO)₄] with AgClO₄ in acetone at room temperature for 10 min, followed by addition of 1鈥?b>7 and stirring at room temperature for 10 h, gave the novel heterobimetallic palladium鈥搑hodium compounds 1a鈥?b>7a as 1:1 electrolytes, where the new bidentate [N,S] palladacycle metalloligands are bonded to the second metal through the pyridine nitrogen atom, and the sulfur atom of the thiosemicarbazone moiety; they exhibit a six-membered bimetallic central ring of differing atoms. In a similar manner, reaction of [PdBr₂(Ph₂PR⁴PPh₂)] (R⁴ = CH₂, C鈺怌H₂, (CH₂)₂, cis-CH鈺怌H) with AgClO₄ in acetone at room temperature, followed by addition of 1鈥?b>7, gave the homobimetallic palladium鈥損alladium compounds, 2b, 3b, 5b鈥?b>7b, and 5c鈥?b>7c, as 1:2 electrolytes, also with [N,S] coordination of the corresponding metalloligand. ¹H鈥?sup>15N HMBC experiments were a most valuable tool in helping to unequivocally ascertain rhodium鈥搉itrogen and palladium鈥搉itrogen coordination in the bimetallic species. The crystal and molecular structures of 3, 6, 2b, and 3b have been determined by X-ray crystallography; for compounds 3 and 3b, inter- and intramolecular interactions in the solid state result in crystal self-organization, leading to chains and/or layers in the molecular array.