Synthesis and Characterization of Functionally Substituted Cyclopentadienyl Derivatives of Silver and Copper
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- 作者：Linda Lettko and Marvin D. Rausch
- 刊名：Organometallics
- 出版年：2000
- 出版时间：October 2, 2000
- 年：2000
- 卷：19
- 期：20
- 页码：4060 - 4065
- 全文大小：74K
- 年卷期：v.19,no.20(October 2, 2000)
- ISSN：1520-6041
文摘
A series of functionally substituted cyclopentadienyl derivatives of silver and copper havebeen synthesized and characterized. Reactions between sodium acetyl- or carbomethoxycyclopentadienylide, triphenylphosphine, and silver triflate (AgSO3CF3) in DME produced Ag[C5H4C(O)CH3](PPh3) and Ag[C5H4CO2CH3](PPh3) in yields of 57-58%. Corresponding copperanalogues were prepared using [BrCu(PPh3)]4. Similar reactions between sodium acetyl- orcarbomethoxycyclopentadienylide and AgSO3CF3 in the presence of the bidentate ligand 1,2-bis(diphenylphosphino)ethane afforded the chelated compounds Ag[C5H4C(O)CH3][Ph2P(CH2)2PPh2] and Ag[C5H4CO2CH3][Ph2P(CH2)2PPh2] in 55-72% yields. Dinuclear compounds ofthe type [Ag(C5H4PPh2)(PR3)]2 (R = Ph, Et) resulted in 36-49% yield from reactions of silverchloride with the appropriate phosphine in refluxing toluene, followed by cooling to -78 
deg.gif">Cand subsequent reactions with lithium diphenylphosphinocyclopentadienide. The compoundsM(C5Ph5)(PEt3) (M = Ag, Cu) containing five bulky phenyl substituents were obtained in44-56% yield from reactions of sodium pentaphenylcyclopentadienide and [ClM(PEt3)]4 inTHF. In general, the new organosilver compounds containing functional substituents onthe cyclopentadienyl ring as well as binuclear phosphine derivatives exhibited enhancedthermal and oxidative stabilities compared with the parent compound Ag(C5H5)(PPh3). 31PNMR studies of the compounds have been undertaken and are in agreement with theproposed structures.
deg.gif">Cand subsequent reactions with lithium diphenylphosphinocyclopentadienide. The compoundsM(C5Ph5)(PEt3) (M = Ag, Cu) containing five bulky phenyl substituents were obtained in44-56% yield from reactions of sodium pentaphenylcyclopentadienide and [ClM(PEt3)]4 inTHF. In general, the new organosilver compounds containing functional substituents onthe cyclopentadienyl ring as well as binuclear phosphine derivatives exhibited enhancedthermal and oxidative stabilities compared with the parent compound Ag(C5H5)(PPh3). 31PNMR studies of the compounds have been undertaken and are in agreement with theproposed structures.