Binuclear iron-manganese acetyl and hydride complexes from the reactions of Cp(CO)2FePPh2 with CH3Mn(CO)5 and HMn(CO)5

Richard P. Rosen, Jeffrey B. Hoke, Robert R. Whittle, Gregory L. Geoffroy, John P. Hutchinson, Jon A Zubieta

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Abstract

The new heterobimetallic bridging acetyl complex Cp(CO)Fe(μ-C(O)CH3)(μ-PPh2)Mn(CO)4 (1) has been prepared by the reaction of CH3Mn(CO)5 with PPh2FeCp(CO)2. It has been spectroscopically and structurally characterized. Complex 1 crystallizes in the space group P1 with a = 11.485 (4) Å, b = 12.989 (4) Å, c = 16.932 (5) Å, α = 68.22 (2)°, β = 87.17 (2)°, γ = 88.88 (2)°, V = 2342 (1) Å, and Z = 4. The structure has been refined to R = 0.044 and Rw = 0.042 for the 3353 reflections with I > 3σ(I). The acetyl ligand bridges the Fe and Mn centers with the acetyl carbon attached to Fe and the oxygen bound to Mn. The nonbonded metals (Fe⋯Mn = 3.718 Å) are also bridged by the μ-PPh2 ligand. The chemistry of complex 1 has been examined with HBF4, [(CH3)3O]BF4, [Ph3C]BF4, H2, PPh2Me, and MeLi, and these reactions are discussed. Reaction of HMn(CO)5 with PPh2FeCp(CO)2 gives the bridging hydride complex Cp(CO)Fe(μ-H)(μ-PPh2)Mn(CO)4 (3), which has also been structurally characterized. It crystallizes in the monoclinic space group P21/n with a = 10.795 (4) Å, b = 13.931 (2) Å, c = 14.497 (4) Å, β = 102.08 (3)°, V = 2132 (2) Å3, and Z = 4. The structure has been refined for the 2412 reflections with I > 2σ(I) to R = 0.057 and Rw = 0.063. The Fe and Mn atoms are separated by 2.806 (1) Å and are bridged by the hydride and the μ-PPh2 ligand. The Fe atom is further coordinated by the Cp ligand and one CO, and Mn has four additional CO ligands.

Original languageEnglish (US)
Pages (from-to)846-855
Number of pages10
JournalOrganometallics
Volume3
Issue number6
StatePublished - 1984
Externally publishedYes

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Rosen, R. P., Hoke, J. B., Whittle, R. R., Geoffroy, G. L., Hutchinson, J. P., & Zubieta, J. A. (1984). Binuclear iron-manganese acetyl and hydride complexes from the reactions of Cp(CO)2FePPh2 with CH3Mn(CO)5 and HMn(CO)5 . Organometallics, 3(6), 846-855.