Verpekin Victor V, Semeikin Oleg V, Vasiliev Alexander D, Kondrasenko Alexander A, Belousov Yuri A, Ustynyuk Nikolai A
Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk Research Center, Siberian Branch of the Russian Academy of Sciences Akademgorodok 50-24 Krasnoyarsk 660036 Russian Federation
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences ul. Vavilova 28 Moscow 119991 Russian Federation
RSC Adv. 2020 Apr 30;10(29):17014-17025. doi: 10.1039/d0ra02333g. eCollection 2020 Apr 29.
The reactions between terminal ethynylpyridines, (trimethylsilyl)ethynylpyridines and cyclopentadienyliron dicarbonyl iodide were studied under Pd/Cu-catalyzed conditions to develop a synthetic approach to the σ-alkynyl iron complexes Cp(CO)Fe-C[triple bond, length as m-dash]C-R (R = -, -, -pyridyl). Depending on the catalyst and reagents used, the yields of the desired σ-pyridylethynyl complexes varied from 40 to 95%. In some cases the reactions with -ethynylpyridine gave as byproduct the unexpected binuclear FePd μ-pyridylvinylidene complex [Cp(CO)Fe{μ-η(C):η(C)-κ(N)-C[double bond, length as m-dash]C(H)(-CHN)}(μ-CO)PdI]. The conditions, catalysts, and reagents that provide the highest yields of the desired σ-pyridylethynyl iron compounds were determined. The methods developed allowed the synthesis of the corresponding σ-4-benzothiadiazolylethynyl complex Cp(CO)Fe-C[triple bond, length as m-dash]C-(4-CHNS) as well. Eventually, synthetic approaches to σ-alkynyl iron complexes of the type Cp(CO)Fe-C[triple bond, length as m-dash]C-R (R = -, -, -pyridyl, 4-benzothiadiazol-2,1,3-yl) based on the Pd/Cu-catalyzed cross-coupling reactions were elaborated.
研究了在钯/铜催化条件下，末端乙炔基吡啶、（三甲基硅基）乙炔基吡啶与环戊二烯基二羰基碘化铁之间的反应，以开发一种合成σ-炔基铁配合物Cp(CO)Fe-C≡C-R（R = -，-，-吡啶基）的方法。根据所使用的催化剂和试剂，所需的σ-吡啶基乙炔基配合物的产率在40%至95%之间变化。在某些情况下，与-乙炔基吡啶的反应会产生意外的双核FePd μ-吡啶基亚乙烯基配合物[Cp(CO)Fe{μ-η(C):η(C)-κ(N)-C═C(H)(-CHN)}(μ-CO)PdI]作为副产物。确定了能提供最高产率的所需σ-吡啶基乙炔基铁化合物的条件、催化剂和试剂。所开发的方法还允许合成相应的σ-4-苯并噻二唑基乙炔基配合物Cp(CO)Fe-C≡C-(4-CHNS)。最终，基于钯/铜催化的交叉偶联反应，阐述了合成Cp(CO)Fe-C≡C-R（R = -，-，-吡啶基，4-苯并噻二唑-2,1,3-基）类型的σ-炔基铁配合物的方法。
