Triazaphospholes versus Triazoles: An Investigation of the Differences between “Click”-Derived Chelating Phosphorus- and Nitrogen-Containing Heterocycles

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• 作者：Julian A. W. Sklorz ; Santina Hoof ; Michael G. Sommer ; Fritz Wei?er ; Manuela Weber ; Jelena Wiecko ; Biprajit Sarkar ; Christian Müller
• 刊名：Organometallics
• 出版年：2014
• 出版时间：January 27, 2014
• 年：2014
• 卷：33
• 期：2
• 页码：511-516
• 全文大小：369K
• ISSN：1520-6041

文摘

A new class of pyridyl-functionalized triazaphospholes bearing either ^tBu or SiMe₃ substituents at the 5-position of the N₃PC heterocycle have been prepared via the 鈥渃lick鈥?reaction starting from 2-(azidomethyl)pyridine and the corresponding phosphaalkynes. In order to investigate the electronic structure and donor鈥揳cceptor properties of such novel chelating and low-coordinate phosphorus heterocycles, calculations at the DFT level have been carried out. Moreover, cyclic voltammetry measurements were performed and the results were compared with those for the structurally related triazole-based systems, demonstrating a significant influence of the phosphorus atom as well as the substitution pattern on the electronic properties of the novel compounds. The P,N hybrid ligands form Re(I) complexes of the type [(N^mN)Re(CO)₃Br] via coordination of the nitrogen atom N² to the metal center rather than via the phosphorus atom, as verified crystallographically.