Selenophosphine Derivatives with Pendant Electron-Rich Fe(魏2-dppe)(畏5-C5Me5)C鈮鈥?Substituents

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• 作者：Ayham Tohm茅 ; Hiba Sahnoune ; Thierry Roisnel ; Vincent Dorcet ; Jean-Fran莽ois Halet ; Fr茅d茅ric Paul
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 14, 2014
• 年：2014
• 卷：33
• 期：13
• 页码：3385-3398
• 全文大小：642K
• ISSN：1520-6041

文摘

Five new selenophosphines (5a鈥?b>d and 7) bearing organometallic Fe(魏²-dppe)(畏⁵-C₅Me₅)C鈮鈥?substituents were synthesized and structurally characterized in order to determine the steric and electronic parameters of the parent metallo-phosphines (1a鈥?b>d and 2). Their cone angles were estimated from available structural data, and their electronic parameters were derived from the ¹J_PSe coupling constants. DFT calculations suggest that ¹J_PSe constants can be used to determine their electronic parameters in spite of the existence of the low-lying excited states for 5a鈥?b>d. Strong solvent effects were evidenced on ¹J_PSe, stressing the need to use a single solvent (CDCl₃) for measuring these coupling constants if comparison of the electronic parameter of these with existing data is sought. Among the parent metallo-phosphines, 2 appears to be the most electron donating ligand by far. According to its ¹J_PSe value, it resembles a tris(alkyl)phosphine but presents a significantly larger Tolman cone angle (胃_T 鈮?172掳) than PPh₃ (胃_T 鈮?145掳).