Catalyzed M–C coupling reactions in the synthesis of σ-(pyridylethynyl)dicarbonylcyclopentadienyliron complexes

Abstract

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)₂Fe–CC–R (R = ortho-, meta-, para-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 ortho-ethynylpyridine gave as byproduct the unexpected binuclear FePd μ-pyridylvinylidene complex [Cp(CO)Fe{μ₂-η¹(C_α):η¹(C_α)-κ¹(N)-C_αC_β(H)(o-C₅H₄N)}(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)₂Fe–CC–(4-C₆H₃N₂S) as well. Eventually, synthetic approaches to σ-alkynyl iron complexes of the type Cp(CO)₂Fe–CC–R (R = ortho-, meta-, para-pyridyl, 4-benzothiadiazol-2,1,3-yl) based on the Pd/Cu-catalyzed cross-coupling reactions were elaborated.