Comparative Oxidative Addition of Transition-Metal Iodocyclopentadienyl Complexes (5-C5H4-I)MLb
详细信息 查看全文
- 作者：Christian Amatore ; Bé ; atrice Godin ; Anny Jutand ; Benoit Ferber ; Siden Top ; Gé ; rard Jaouen
- 刊名：Organometallics
- 出版年：2007
- 出版时间：July 16, 2007
- 年：2007
- 卷：26
- 期：15
- 页码：3887 - 3890
- 全文大小：71K
- 年卷期：v.26,no.15(July 16, 2007)
- ISSN：1520-6041
文摘
The rate constants of the oxidative addition of thetransition-metal iodocyclopentadienyl complexes (
BORDER=0 >5-C5H4-I)MLn (MLn = Mn(CO)3 (1a), Re(CO)3 (1b), CpFe (1c)) withPd0(PPh3)4 have been determined in DMF. As expected, theoxidative addition is faster for the electron-acceptor groups Mn(CO)3 and Re(CO)3 than for the electron-donor group FeCp,with the reactivity order 1a > 1b 
1c. Comparison of therate constants of the oxidative additions affords a new strategyfor the evaluation of the electronic properties of transition-metal units ligated to the iodocyclopentadienyl moiety with thefollowing decreasing electron-acceptor properties: Mn(CO)3> Re(CO)3 FeCp. The complexes formed in the oxidativeaddition are characterized as trans-[(5-C5H4)PdI(PPh3)2]MLn(MLn = Mn(CO)3 (2a), Re(CO)3 (2b), CpFe (2c)) with thedecreasing stability order in DMF: 2c 2b > 2a. Therelevance to the efficiency of palladium-catalyzed Stille orSonogashira reactions from related complexes 1 is discussed.
BORDER=0 >5-C5H4-I)MLn (MLn = Mn(CO)3 (1a), Re(CO)3 (1b), CpFe (1c)) withPd0(PPh3)4 have been determined in DMF. As expected, theoxidative addition is faster for the electron-acceptor groups Mn(CO)3 and Re(CO)3 than for the electron-donor group FeCp,with the reactivity order 1a > 1b 1c. Comparison of therate constants of the oxidative additions affords a new strategyfor the evaluation of the electronic properties of transition-metal units ligated to the iodocyclopentadienyl moiety with thefollowing decreasing electron-acceptor properties: Mn(CO)3> Re(CO)3 FeCp. The complexes formed in the oxidativeaddition are characterized as trans-[(5-C5H4)PdI(PPh3)2]MLn(MLn = Mn(CO)3 (2a), Re(CO)3 (2b), CpFe (2c)) with thedecreasing stability order in DMF: 2c 2b > 2a. Therelevance to the efficiency of palladium-catalyzed Stille orSonogashira reactions from related complexes 1 is discussed.