Functionalization of Cp4Fe4(CO)4: Contrasts and Comparisons with Ferrocene
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- 作者：Mark D. Westmeyer ; Mark A. Massa ; Thomas B. Rauchfuss ; and Scott R. Wilson
- 刊名：Journal of the American Chemical Society
- 出版年：1998
- 出版时间：January 14, 1998
- 年：1998
- 卷：120
- 期：1
- 页码：114 - 123
- 全文大小：266K
- 年卷期：v.120,no.1(January 14, 1998)
- ISSN：1520-5126
文摘
Thermolysis of a xylene solution ofCp2Fe2(CO)4 andPPh3 yields primarilyCp4Fe4(CO)4 (1)togetherwith smaller amounts of(C5H4Ph)Cp3Fe4(CO)4andCp3Fe3(CO)3(PPh2).Cluster 1 can be alkylated and arylatedby using organolithium reagents to give the derivatives(C5H4R)Cp3Fe4(CO)4.This reaction is competitivewith reduction of 1 by the organolithium reagent. Amore versatile method for functionalizing 1 involvesitsdeprotonation with lithium diisopropylamide (LDA) followed by treatmentwith electrophiles to give(C5H4X)Cp3Fe4(CO)4(X = C(OH)HCH3, CO2H, CHO, SPh,PPh2). An excess of LDA gave increasedamountsof the di- and even trifunctionalized derivatives(C5H4X)xCp4-xFe4(CO)4(x = 2, 3). Treatment of(C5H4CHO)Cp3Fe4(CO)4 withthe lithiated cluster gave the double cluster[(C5H4)Cp3Fe4(CO)4]2CHOH.The useof the cluster as a ligand was demonstrated by the synthesis of theadducts(C5H4PPh2MLn)Cp3Fe4(CO)4,where MLn = RuCl2(cymene),IrCl(1,5-C8H12). Single-crystal X-raydiffraction was employed to characterize[(C5H4)Cp3Fe4(CO)4]2CHOHand(C3H4PPh2)Cp3Fe4(CO)4RuCl2(cymene).