Electronic Structure and Evolution of a Terminal Butadienylphosphinidene Complex
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- 作者：Ngoc Hoa Tran Huy ; Shaojie Hao ; Louis Ricard ; and Franç ; ois Mathey
- 刊名：Organometallics
- 出版年：2006
- 出版时间：June 19, 2006
- 年：2006
- 卷：25
- 期：13
- 页码：3152 - 3155
- 全文大小：232K
- 年卷期：v.25,no.13(June 19, 2006)
- ISSN：1520-6041
文摘
The DFT study of the 1-butadienylphosphinidene complex [CH2=CHCH=CHP-Cr(CO)5] shows adelocalized structure with a short P-C bond at 1.789 Å and a long C
=C
double bond at 1.367 Å. TheW(CO)5 complex has been synthesized by copper-catalyzed decomposition of the appropriate 7-phosphanorbornadiene complex. It gives the normal reaction products with alkynes (phosphirenes) and withconjugated dienes (phospholenes and dihydrophosphepines via a phospha-Cope rearrangement), but whenno trapping reagent is added to the reaction mixture, it gives a complex pentacyclic product whose structurehas been established by X-ray crystal structure analysis and whose formation involves a cascade of reactionsstarting at the dienyl substituent of the precursor.
=C double bond at 1.367 Å. TheW(CO)5 complex has been synthesized by copper-catalyzed decomposition of the appropriate 7-phosphanorbornadiene complex. It gives the normal reaction products with alkynes (phosphirenes) and withconjugated dienes (phospholenes and dihydrophosphepines via a phospha-Cope rearrangement), but whenno trapping reagent is added to the reaction mixture, it gives a complex pentacyclic product whose structurehas been established by X-ray crystal structure analysis and whose formation involves a cascade of reactionsstarting at the dienyl substituent of the precursor.