Abstract
The reaction of [Fe 2(η-C 5H 5) 2(CO) 3(CNR)] with R′OSO 2CF 3 (R,R′ Me or Et) gives a mixture of cis and trans-[Fe 2(η-C 5H 5) 2(CO) 2(μ-CO)μ-CN(R′)R]SO 3CF 3. When R R′ Me the isomer ratio is variable, but the cis always predominates and is the only product when R ≠ R′. The complexes [Fe 2(η-C 5H 5) 2(CO) 2(CNR) 2] react with R′OSO 2CF 3 and the more reactive alkyl halides R′X to give a mixture of cis- [Fe 2(η-C 5H 5) 2(CO)(CNR)(μ-CO)ν-CN(R′)R]X and cis-[Fe 2(η-C 5 H 5) 2(CO) 2μ-CN(R′)R 2][X] 2. In both series of cations the presence of μ-CN(R′)R ligands give rise to isomers that differ in respect of orientation about the CN bond. The cations are not fluxional and do not undergo cis- trans interconversion, bridge-terminal ligand exchange, or rotation about the μ-CN(R′)R double bond. The structure of the cations in the [Fe 2(η-C 5H 5) 2(CO)(CNMe)(μ-CO)(μ-CNMe 2)]BPh 4 and [Fe 2(η-C 5H 4Me) 2(CO) 2(μ-CNMe 2) 2][SO 3CF 3] 2 salts were confirmed as cis by X-ray diffraction studies. Their dimensions are similar to those previously found in cis- [Fe 2(η-C 5H 4Me) 2(CO) 2(μ-CO)(μ-CNMe 2)]I, but with variations due to the differing acceptor and donor abilities of the various ligands. Infrared and NMR spectra of the complexes are reported and discussed.
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