Organotransition-metal Metallacarboranes 5

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Studies on (η⁶-arene)(carborane)iron complexes of benzene and biphenyl. Crystal structures of (η⁶-C₆H₅C₆H₅)Fe(Et₂C₂B₄H₄) and 1,2-[(η⁶-C₆H₆)Fe(Et₂C₂B₄H₃)]₂CH(CH₃)CH₂, a hydrocarbon-linked bis(ferracarborane)


Full title: Organotransition-metal metallacarboranes. 5. Studies on (η6-arene)(carborane)iron complexes of benzene and biphenyl. Crystal structures of (η6-C6H5-C6H 5)Fe(Et2C2B4H4) and 1,2-[(η6-C6H6)Fe(Et2C 2B4H3)]2CH(CH3)CH 2, a hydrocarbon-linked bis(ferracarborane). The reaction of closo-1,2,3-(η6-C6R6)Fe(Et 2C2B4H4) (R = H, Me) with 1,2-(NMe2)2(CH2)2 gave nido-(η6-C6R6)Fe(Et2C 2B3H5) species in high yield. Bridge deprotonation of the nido product (R = H) with KH followed by metal-promoted oxidative fusion formed (η6-C6H6)Fe(Et4C 4B6H6), which was structurally characterized from two-dimensional (2-D) 11B-11B NMR spectra and X-ray evidence as an 11-vertex FeC4B6 cage. Treatment of (η6-C6H6)Fe(Et2C 2B4H4) with naphthalene over Al and AlCl3 gave several low-yield products, one of which was characterized by X-ray diffraction as a 1,2-bis((arene)ferracarboranyl)propane derivative. The reaction of (η6-C8H10)Fe(Et2C 2B4H4) with biphenyl in vacuo at 200°C gave (η6-C6H6-C6H 6)Fe(Et2C2B4H4) in 44% yield; the same complex was also obtained in lower yield via ligand exchange in hexane over Al and AlCl3. The structure of the biphenyl complex was established via X-ray crystallography. Treatment of this compound with a second equivalent of (η6-C8H10)Fe(Et2C 2B4H4) at 180 °C in vacuo gave (Et2C2B4H4)Fe(η 6-C6H5)(η6-C6H 5)Fe(Et2C2B4H4), characterized spectroscopically. Crystal data for 1,2-[(η6-C6H6)Fe(Et2C 2B4H3)]2CH(CH3)CH 2: Mr = 567, space group P21/n, Z = 2, a = 8.062 (2) Å, b = 15.335 (3) Å, c = 12.661 (3) Å, β = 105.99 (2)°, V = 1504 Å3, R = 0.050 for 2254 reflections for which Fo 2 > 3σ(Ro 2). Crystal data for (η6-C6H5-C6H 5)Fe(Et2C2B4H4): Mr = 339, space group P21/c, Z = 4, a = 9.906 (2) Å, b = 12.678 (3) Å, c = 14.495 (4) Å, β = 100.94 (2)°, V = 1787 Å3, R = 0.047 for 3053 reflections having Fo 2 > 3σ(Fo 2). © 1985 American Chemical Society.



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© 1985 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jan 1985