Mono-, Di-, and Triborylphosphine Analogues of Triarylphosphines

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• 作者：Jonathan A. Bailey ; Marten Ploeger ; Paul G. Pringle
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 21, 2014
• 年：2014
• 卷：53
• 期：14
• 页码：7763-7769
• 全文大小：338K
• ISSN：1520-510X

文摘

Diazaborinylphosphines based on the 1,8-diaminonaphthylboronamide heterocycle are prepared by a chlorosilane-elimination reaction, and their structural and bonding properties are compared to those of PPh₃. The precursor chloroborane ClB{1,8-(NH)₂C₁₀H₆} (I) is fully characterized including its crystal structure, which features intermolecular 蟺鈥撓€ stacking, B路路路N interactions, and N鈥揌路路路Cl hydrogen bonding. Treatment of I with Ph_3鈥?i>nP(SiMe₃)_n gave the corresponding Ph_3鈥?i>nP(B{1,8-(NH)₂C₁₀H₆})_n, {L₁ (n = 1), L₂ (n = 2), and L₃ (n = 3)}. The crystal structures of L_1鈥?b>3 reveal an increase in the planarity at P as a function of n, and the steric bulk of the diazaborinyl substituent B{1,8-(NH)₂C₁₀H₆} is similar to that of a phenyl. Nucleus-independent chemical shift calculations were carried out that suggest that the 14 蟺-electron diazaborinyl substituent can be described as aromatic overall, though the BN₂-containing ring is slightly antiaromatic. The complexes cis-[Mo(L_1鈥?b>3)₂(CO)₄] (1鈥?b>3) are prepared from [Mo(nbd)(CO)₄] (nbd = norbornadiene) and L_1鈥?b>3. From the position of the 谓(CO) (A₁) band in the IR spectra of 1鈥?b>3, it is deduced that the diazaborinyl substituent has a donating capacity similar to an alkyl group.