Phosphinoalkyne Additions to (5-C5H5)2Rh2(
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- 作者：Ron S. Dickson ; Tania de Simone ; Richard J. Parker ; and Gary D. Fallon
- 刊名：Organometallics
- 出版年：1997
- 出版时间：April 15, 1997
- 年：1997
- 卷：16
- 期：8
- 页码：1531 - 1537
- 全文大小：377K
- 年卷期：v.16,no.8(April 15, 1997)
- ISSN：1520-6041
文摘
The phosphinoalkynes Ph2PC
CR (R =H, Me, CF3, But, Ph, and PPh2)behave as tertiaryphosphines in their reactions with the dirhodium complex(
5-C5H5)2Rh2(
-CO)(-2:2-CF3C2CF3) (1). All six addition products(5-C5H5)2Rh2(CO)(-1:1-CF3C2CF3)(1-Ph2PCCR)(4)have been isolated and fully characterized. Thebis(diphenylphosphino)alkynePh2PCCPPh2also forms a tetranuclear complex (5) in which eachphosphorus coordinates to a dirhodiumunit. With the exception of 4 when R = H, the solidcomplexes are relatively stable. However,when solutions of two of the complexes (R = Me, Ph) are left in thepresence of both silicaand oxygen, there is oxygen transfer to an alkyne carbon accompanied byan intramolecularcondensation reaction to generate a phosphino-enone ligand. Thestructure of one of theseoxidation products,(5-C5H5)2Rh2(-C(CF3)C(CF3)C{C(O)R}PPh2)(6, R = Ph), has beenestablished by X-ray crystallography. Prior oxidation of thephosphinoalkynes to give Ph2P(O)CCR and subsequent reaction with 1 leads to theformation of typical alkyne additionproducts.
CR (R =H, Me, CF3, But, Ph, and PPh2)behave as tertiaryphosphines in their reactions with the dirhodium complex(5-C5H5)2Rh2(-CO)(-2:2-CF3C2CF3) (1). All six addition products(5-C5H5)2Rh2(CO)(-1:1-CF3C2CF3)(1-Ph2PCCR)(4)have been isolated and fully characterized. Thebis(diphenylphosphino)alkynePh2PCCPPh2also forms a tetranuclear complex (5) in which eachphosphorus coordinates to a dirhodiumunit. With the exception of 4 when R = H, the solidcomplexes are relatively stable. However,when solutions of two of the complexes (R = Me, Ph) are left in thepresence of both silicaand oxygen, there is oxygen transfer to an alkyne carbon accompanied byan intramolecularcondensation reaction to generate a phosphino-enone ligand. Thestructure of one of theseoxidation products,(5-C5H5)2Rh2(-C(CF3)C(CF3)C{C(O)R}PPh2)(6, R = Ph), has beenestablished by X-ray crystallography. Prior oxidation of thephosphinoalkynes to give Ph2P(O)CCR and subsequent reaction with 1 leads to theformation of typical alkyne additionproducts.