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• 作者：Marta Mari帽o ; Javier Mart铆nez ; Marcelo Caama帽o ; M^a Teresa Pereira ; Juan M. Ortigueira ; Eduardo Gayoso ; Alberto Fern谩ndez ; Jos茅 M. Vila
• 刊名：Organometallics
• 出版年：2012
• 出版时间：February 13, 2012
• 年：2012
• 卷：31
• 期：3
• 页码：890-894
• 全文大小：232K
• 年卷期：v.31,no.3(February 13, 2012)
• ISSN：1520-6041

文摘

Reaction of the Schiff base ligands CpFe[畏⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)鈺怤R] (R = 2,4,6-Me₃C₆H₂, a; R = Cy, b) derived from the 1,2-disubstituted formylferrocene CpFe[(CHO){C(H)O(CH₂)₃O}-畏⁵-C₅H₃] 1, with Li₂[PdCl₄] in methanol at room temperature for 48 h, gave the chlorine-bridged complexes [Pd{CpFe[畏⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)鈺怤R]}(Cl)]₂, 1a and 1b, after C鈥揌 activation of the cyclopentadienyl ring bearing the cyclic acetal. The reactions of 1a and 1b with the Ph₂P(CH₂)_nPPh₂ diphosphines in a 1:2 ratio, plus addition of ammonium hexafluorophosphate, gave the dinucelar compounds [Pd{CpFe[畏⁵-C₅H₂{C(H)O(CH₂)₃O}C(H)鈺怤R]}-(Ph₂P(CH₂)_nPPh₂-P,P)][PF₆] 2a, 3a and 2b, 3b with the diphosphine in a chelating mode, as 1:1 electrolytes. Treatment of the latter with aqueous acetic acid gave the corresponding functionalized compounds with transformation of the 1,3-dioxane ring into a formyl group on the metalated ring, 4a, 5a and 4b, 5b.
The Schiff base condensation reaction of 5b with 2-(methylthio)aniline in refluxing chloroform gave [Pd(Ph₂P(CH₂)₂PPh₂){(CpFe)畏⁵-C₅H₂[C(H)鈺怤Cy][C(H)鈺怤(2-SMeC₆H₄]}][PF₆] 6b, with regeneration of the C鈺怤 double bond, which, when treated with lithium tetrachloropalladate in methanol for 48 h, gave the novel compound [Pd(Ph₂P(CH₂)₂PPh₂){(CpFe)畏⁵-C₅H[C(H)鈺怤Cy][C(H)鈺怤(2-SMeC₆H₄]}PdCl][PF₆] 7b, which is the first ferrocene metallacycle displaying 1,3-double cyclopalladation.