Growing the Molecular Architecture at Alkynyl(amino)carbene Ligands in Diiron µ-Aminocarbyne Complexes

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• 作者：Fabio Marchetti ; Stefano Zacchini and Valerio Zanotti
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：October 2016
• 年：2016
• 卷：2016
• 期：29
• 页码：4820-4828
• 全文大小：1967K
• ISSN：1099-0682c

文摘

The diiron µ-aminocarbyne imidoyl complexes [Fe₂{µ-CN(Me)(R)}(µ-CO)(CO){C(C≡CR′)=NXyl}Cp₂] [R = Xyl, R′ = Ph (1a);[1] R = Xyl, R′ = Tol (1b);[1] R = Me, R′ = Ph (1c); R = Me, R′ = SiMe₃ (1d); Xyl = 2,6-C₆H₃Me₂, Tol = 4-C₆H₄Me] have been prepared by the addition of lithium acetylides to precursors containing a terminal isocyanide ligand. The treatment of 1a–c with CF₃SO₃CH₃ afforded the alkynyl(amino)carbene derivatives [Fe₂{µ-CN(Me)(R)}(µ-CO)(CO){C(C≡CR′)N(Me)(Xyl)}Cp₂][SO₃CF₃] [R = Me, R′ = Ph (2a); R = Xyl, R′ = Ph (2b); R = Xyl, R′ = Tol (2c)] in high yields. The reactions of 2b,c with CH₃OH/NaBF₄, NH₂R and NaBH₄ led to [Fe₂{µ-CN(Me)(Xyl)}(µ-CO)(CO){C(CH=C(Ph)OMe)N(Me)(Xyl)}Cp₂][BF₄] (3), [Fe₂{µ-CN(Me)(Xyl)}(µ-CO)(CO){C(CH=C(Tol)NHR)N(Me)(Xyl)}Cp₂][SO₃CF₃] [R = Et (4a); R = Ph (4b)], and [Fe₂{µ-CN(Me)(Xyl)}(µ-CO)(CO){C(CH=CHTol)N(Me)(Xyl)}Cp₂][SO₃CF₃] (5) in yields of 65–80 %. Complexes 3–5 were formed by the selective functionalization of the alkynyl group in 2b,c. Complex 2c reacted with NaCH(CN)₂/CH₂(CN)₂ and NaCH(CO₂Me)₂ to yield [Fe₂{µ-CN(Me)(Xyl)}(µ-CO)(CO){C{N(Me)(Xyl)}CH=C(Tol)C(CN)C(NH₂)C(CN)₂}Cp₂] (6) and [Fe₂{µ-C(NXyl)C(C(Tol)=C(CO₂Me)₂)CN(Me)(Xyl)}(µ-CO)₂Cp₂] (7) in yields of 65 and 60 %, respectively. All the products were purified by alumina chromatography, alumina being presumably involved in the formation of 3, and characterized by elemental analysis and IR and NMR spectroscopy. The structures of 2b, 3, 5, and 6 were ascertained by single-crystal X-ray diffraction analysis.