Versatile Coordination Behavior of Aryl-Substituted Phosphiniminate and Phosphoranate Anions: Synthesis and Structural Characterization of Lithium Complexes with 
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- 作者：Musa Said ; Mark Thornton-Pett ; and Manfred Bochmann
- 刊名：Organometallics
- 出版年：2001
- 出版时间：December 24, 2001
- 年：2001
- 卷：20
- 期：26
- 页码：5629 - 5635
- 全文大小：127K
- 年卷期：v.20,no.26(December 24, 2001)
- ISSN：1520-6041
文摘
Metalation of the bulky phosphinimine 4-MeC6H4CH(SiMe3)P(Ph)2=NSiMe3 (1) withn-butyllithium followed by recrystallization from benzene affords [Li{4-MeC6H4C(SiMe3)P(Ph)2=NSiMe3}]2 (3), while Li(THF)2{4-MeC6H4C(SiMe3)P(Ph)2=NSiMe3} (2) is formed inthe presence of THF. Similarly, treatment of the N-mesityl compound 4-ButC6H4CH(SiMe3)P(Ph)2=NC6H2Me3-2,4,6 (4) with BunLi in the presence of THF produced Li(THF)2{4-ButC6H4C(SiMe3)P(Ph)2=NC6H2Me3-2,4,6} (5), while lithiation of the new phosphorus ylid 4-ButC6H4CH2P(Ph)2{=C(SiMe3)C6H4But-4} (6) afforded Li(THF)2{4-ButC6H4CHP(Ph)2C(SiMe3)C6H4But-4} (7). The solid-state structures of 2, 3, 5, and 7 were determined. Whereas the anionin 2 acts simply as a C-N chelate, the MeC6H4 moieties in the dimeric compound 3 are
6-bonded. On the other hand, compound 5 contains an aryl substituent that is 1-coordinatedto Li+ via its ipso-carbon, while the ylid anion 7 displays an unusual 1-coordination to oneortho-C atom of a strongly tilted arene ring. The results demonstrate the surprisingly variablecoordination behavior of aryl-substituted [CPN]- and [CPC]- anions and the importance ofaryl substituents in stabilizing electron-deficient metal centers.
6-bonded. On the other hand, compound 5 contains an aryl substituent that is 1-coordinatedto Li+ via its ipso-carbon, while the ylid anion 7 displays an unusual 1-coordination to oneortho-C atom of a strongly tilted arene ring. The results demonstrate the surprisingly variablecoordination behavior of aryl-substituted [CPN]- and [CPC]- anions and the importance ofaryl substituents in stabilizing electron-deficient metal centers.