Functionalization of Cp4Fe4(CO)4: Contrasts and comparisons with ferrocene

Mark D. Westmeyer, Mark A. Massa, Thomas B. Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review


Thermolysis of a xylene solution of Cp2Fe2(CO)4 and PPh3 yields primarily Cp4Fe4(CO)4 (1) together with smaller amounts of (C5H4Ph)Cp3Fe4(CO)4 and Cp3Fe3(CO)3(PPh2). Cluster 1 can be alkylated and arylated by using organolithium reagents to give the derivatives (C5H4R)Cp3Fe4(CO)4. This reaction is competitive with reduction of 1 by the organolithium reagent. A more versatile method for functionalizing 1 involves its deprotonation with lithium diisopropylamide (LDA) followed by treatment with electrophiles to give (C5H4X)Cp3Fe4 (X = C(OH)HCH3, CO2H, CHO, SPh, PPh2). An excess of LDA gave increased amounts of the di- and even trifunctionalized derivatives (C5H4X)(x)Cp(4-x)Fe4(CO)4 (x = 2, 3). Treatment of (C5H4- CHO)Cp3Fe4(CO)4 with the lithiated cluster gave the double cluster [(C5H4)Cp3Fe4(CO)4]2CHOH. The use of the cluster as a ligand was demonstrated by the synthesis of the adducts (C5H4PPh2ML(n))Cp3Fe4(CO)4, where ML(n) = RuCl2(cymene), IrCl(1,5-C8H12). Single-crystal X-ray diffraction was employed to characterize [(C5H4)Cp3Fe4(CO)4]2CHOH and (C3H4PPh2)Cp3Fe4(CO)4RuCl2(cymene).

Original languageEnglish (US)
Pages (from-to)114-123
Number of pages10
JournalJournal of the American Chemical Society
Issue number1
StatePublished - Jan 14 1998

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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