Trans-spanning acetylenic bispyridine ligands: synthesis and structural characterization of novel organic and organometallic pseudodehydroannulenes
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- 作者：Shotwell ; Sandra ; Ricks ; Holly L. ; Morton ; Jason G.M. ; Laskoski ; Matthew ; Fiscus ; Jeff ; Smith ; Mark D. ; et. al.
- 关键词：Alkynes ; Heterocycles ; Metallacycles ; N-Pincer ligands ; Self-assembly ; Iron ; Copper ; C51H37ClCuF3N4O7S
- 刊名：Journal of Organometallic Chemistry
- 出版年：2003
- 出版时间：April 1, 2003
- 年：2003
- 卷：671
- 期：1-2
- 页码：43-51
- 全文大小：509 K
文摘
The synthesis of a novel ferrocene based pincer ligand C5H5-Fe[C5H3(-
-C5H4N)2] is reported. This pincer ligand was prepared by the Pd-catalyzed reaction of 1,2-diethynylferrocene with 2-iodopyridine. The complex is a trans-spanning ligand and analogous to 1,2-bis(2-pyridinylethynyl)-4,5-dimethoxybenzene. A series of trans-coordinated 1:1 or 2:1 complexes (empirical formulae C51H37ClCuF3N4O7S and C23H18Cl4N2O2Pd) that form from the ligands and (CH3CN)2PdCl2 or Cu(OTf)2 were obtained. These complexes form 13-membered rings. Structurally these complexes resemble a hexadehydro[14]annulene in which two benzene groups are replaced by pyridine rings and one alkyne group is replaced by the co-ordinated metal. All of the trans-spanning complexes were characterized by single crystal X-ray diffraction. Their molecular and solid-state structures are discussed. The Pd-complexes are of interest as potential high activity catalysts for Sonogashira-type couplings of alkynes to aryl halides. The 1,2-(bis-2′-pyridylethyn-1′-yl)ferrocene, was crystallized with PdCl2 to obtain a novel organometallic trans-spanning complex of the formula C24H16Cl2FeN2Pd that was crystallographically characterized.
-C5H4N)2] is reported. This pincer ligand was prepared by the Pd-catalyzed reaction of 1,2-diethynylferrocene with 2-iodopyridine. The complex is a trans-spanning ligand and analogous to 1,2-bis(2-pyridinylethynyl)-4,5-dimethoxybenzene. A series of trans-coordinated 1:1 or 2:1 complexes (empirical formulae C51H37ClCuF3N4O7S and C23H18Cl4N2O2Pd) that form from the ligands and (CH3CN)2PdCl2 or Cu(OTf)2 were obtained. These complexes form 13-membered rings. Structurally these complexes resemble a hexadehydro[14]annulene in which two benzene groups are replaced by pyridine rings and one alkyne group is replaced by the co-ordinated metal. All of the trans-spanning complexes were characterized by single crystal X-ray diffraction. Their molecular and solid-state structures are discussed. The Pd-complexes are of interest as potential high activity catalysts for Sonogashira-type couplings of alkynes to aryl halides. The 1,2-(bis-2′-pyridylethyn-1′-yl)ferrocene, was crystallized with PdCl2 to obtain a novel organometallic trans-spanning complex of the formula C24H16Cl2FeN2Pd that was crystallographically characterized.