N鈥揚 Bond Cleavage Induced Ring Formation of Cyclosilazanes from Reactions of Aryl(phosphanyl)aminotrichlorosilanes with Lithium Alkynyls

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• 作者：Jinjin Wang ; Rui Liu ; Wenqing Ruan ; Yan Li ; Kartik Chandra Mondal ; Herbert W. Roesky ; Hongping Zhu
• 刊名：Organometallics
• 出版年：2014
• 出版时间：June 9, 2014
• 年：2014
• 卷：33
• 期：11
• 页码：2696-2703
• 全文大小：415K
• 年卷期：v.33,no.11(June 9, 2014)
• ISSN：1520-6041

文摘

The aryl(silyl)aminotrichlorosilane 2,6-iPr₂C₆H₃N(SiMe₂Ph)SiCl₃ (1) and aryl(phosphanyl)aminotrichlorosilane ArN(PPh₂)SiCl₃ (Ar = 2,6-iPr₂C₆H₃ (2), 4-MeC₆H₄ (3), 2,4,6-Me₃C₆H₂ (4)) were prepared and utilized for investigation in reactions with freshly prepared lithium alkynyls. Reaction of 1 with PhC鈮Li resulted in the compounds PhMe₂SiC鈮Ph and 2,6-iPr₂C₆H₃N[Li(THF)₃]Si(C鈮Ph)₃ (5), while 2 reacted with R鈥睠鈮Li to produce the compounds Ph₂PC鈮R鈥?and [2,6-iPr₂C₆H₃NSi(C鈮R鈥?₂]₂ (R鈥?= Ph (6), tBu (7), CH₂CH₂Ph (8)). Reaction of 3 with PhC鈮Li led to the formation of Ph₂PC鈮Ph and [4-MeC₆H₄NSi(C鈮Ph)₂]₃ (9a) as a major product and {4-MeC₆H₄NSi(C鈮Ph)[N(4-MeC₆H₄)Si(C鈮Ph)₃]}₂ (9b) as a minor product. When 4 was reacted with PhC鈮Li, [2,4,6-Me₃C₆H₂NSi(C鈮Ph)₂]₂ (10a) was isolated as the major product while [(2,4,6-Me₃C₆H₂)₃N₃Si₂(C鈮Ph)₄Li(THF)]^{鈭?/sup>[Li(THF)₄]+ (10b) was the minor product. The formation of Ph₂PC鈮Ph was also detected. All reported compounds were characterized by multinuclear NMR (1H, 13C, 29Si, and/or 31P) and/or IR spectroscopy, and compounds 2, 5鈥?b>8, 9a, and 10b were further distinguished by single-crystal X-ray crystallography. These results exhibit a route to the Si₂N₂- or Si₃N₃-based cyclosilazanes 6鈥?b>8, 9a, 9b, and 10a via the N鈥揚 bond cleavage of the aryl(phosphanyl)aminotrichlorosilanes during multiple metathesis reactions.}