Organotransition-metal Metallacarboranes 6

Alternative Title

Synthesis of (CH₂)n-bridged (η⁶-arene)ferracarboranes: Ferrocenophane analogues. Structure of η⁶-C₅H₅(CH₂)₂Fe(C₂B₄H₅)


The ferracarborane (η6-C8H10)Fe([Ph(CH2) 3]C2B4H5) containing a 3-phenylpropyl substituent on a cage carbon atom was prepared and treated with AlCl3/Al to give [η6-C6H5(CH2) 3]Fe(C2B4H5) (3), an air-stable yellow solid containing a trimethylene group bridging the carborane and benzene ligands. Reaction of 3 with CH3OH removed the apex boron of the carborane ligand to give nido-[η6-C6H5(CH2) 3]Fe(C2B3H6) (4). In an attempt to prepare analogous dimethylene-bridged complexes, (η6-C8H10)Fe([Ph(CH2) 2]C2B4H5) was synthesized and treated with AlCl3/Al, but species containing intramolecular bridges were not obtained; instead, the main product was a dimer, [η6-C6H5(CH2) 2Fe(C2B4H5)]2, which is proposed to have a “head-to-tail” structure in which each iron binds to one carborane ligand and to the phenyl group attached (through a -(CH2)2- chain) to the other carborane. The structures of the new compounds were determined via high-resolution 11B, 1H, and 13C NMR, IR, and mass spectra and an X-ray crystal structure analysis of 3. Crystal data: Mr = 247, space group P21/c, Z = 4, a = 13.942 (6) Å, b = 6.311 (3) Å, c = 14.577 (2) Å, β = 111.33 (3)°, V = 1195 Å3, R = 0.039 for 1870 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