Versatile reactivity of dioxaneferrocenylimine palladacycles by controlled acid hydrolysis. Crystal and molecular structure of [Pd{CpFe[¦Ç⁵-C₅H₂{CH(OMe)₂}C(H)N-2,4,6-Me₃C₆H₂]}(Cl

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• 作者：Javier Mart¨ªnez ; Marta Mari?o ; Marcelo Caama?o ; M^a Teresa Pereira ; Juan M. Ortigueira ; Eduardo Gayoso ; Margarita L¨®pez-Torres ; Jos¨¦ M. Vila
• 关键词：Palladium ; Ferrocene ; Schiff base ; Phosphine ; Acetal ; Crystal structure
• 刊名：Journal of Organometallic Chemistry
• 出版年：2013
• 出版时间：15 September, 2013
• 年：2013
• 卷：740
• 期：Complete
• 页码：92-97
• 全文大小：516 K

文摘

Treatment of a or b with Li₂[PdCl₄] in methanol at room temperature for 48?h, gave the tetrametallic chlorine bridged complexes [Pd{CpFe[¦Ç⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)NR]}(¦Ì-Cl)]₂, 1a and 1b, containing a cyclic acetal on the metallated cyclopentadienyl ring. The reactions of 1a and 1b with the Ph₂P(CH₂)_nPPh₂ diphosphines in a 1:1 ratio gave the tetrametallic species [{Pd{CpFe[¦Ç⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)NR]}(Cl)}₂(¦Ì-Ph₂P(CH₂)_nPPh₂)], n?=?1-4 as appropriate, 2a-5a and 2b-5b, with the diphosphine in a bridging mode and terminal chlorine ligands. Treatment of 1a and 1b with monophosphines yielded the dimetallic compounds [Pd{CpFe[¦Ç⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)NR]}(Cl)(L)] (L?=?PPh₃, PPh₂Me, PPh₂Et) 6a-8a and 6b-7b. Reaction of the phosphine derivatives with aqueous acetic acid gave the corresponding functionalized compounds with transformation of the 1,3-dioxane ring into a formyl group on the metallated ring 9a-15a and 9b-14b. Reaction of 8a with acetic acid in methanol gave [Pd{CpFe[¦Ç⁵-C₅H₂{CH(OMe)₂}C(H)N-2,4,6-Me₃C₆H₂]}(Cl)(PPh₂Et)] 16a, after a transacetalization reaction with an acetal moiety -CH(OMe)₂ on the metallated five-membered ring. The molecular structure of compound 16a has been determined by X-ray diffraction analysis.