1356834-41-7Relevant academic research and scientific papers
Dioxaneferrocenylimine cyclometalated compounds as precursors to novel functionalized Di- and tetranuclear metallacycles leading to 1,3-double palladation of an η5-C5H5 ring
Marino, Marta,Martinez, Javier,Caamano, Marcelo,Pereira, Ma Teresa,Ortigueira, Juan M.,Gayoso, Eduardo,Fernandez, Alberto,Vila, Jose M.
, p. 890 - 894 (2012)
Reaction of the Schiff base ligands CpFe[η5-C 5H2{C(H)O(CH2)3O}C(H)=NR] (R = 2,4,6-Me3C6H2, a; R = Cy, b) derived from the 1,2-disubstituted formylferrocene CpFe[(CHO){C(H)O(CH2) 3O}-η5-C5H3] 1, with Li 2[PdCl4] in methanol at room temperature for 48 h, gave the chlorine-bridged complexes [Pd{CpFe[η5-C5H 2{C(H)O(CH2)3O}C(H)=NR]}(Cl)]2, 1a and 1b, after C-H 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[η 5-C5H2{C(H)O(CH2) 3O}C(H)=NR]}-(Ph2P(CH2)nPPh 2-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)η5-C5H 2[C(H)=NCy][C(H)=N(2-SMeC6H4]}][PF 6] 6b, with regeneration of the C=N double bond, which, when treated with lithium tetrachloropalladate in methanol for 48 h, gave the novel compound [Pd(Ph2P(CH2)2PPh2){(CpFe) η5-C5H[C(H)=NCy][C(H)=N(2-SMeC6H 4]}PdCl][PF6] 7b, which is the first ferrocene metallacycle displaying 1,3-double cyclopalladation.
