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Chemical Behaviour of the Mixed-metal Carbonyl Clustrs (1-) and (2-). Crystal Structures of (1-) and >(1-)

DOI: 10.1039/DT9950002763

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2763 - 2768 (1995)

Update date:2022-09-26

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Authors:

Pergola, Roberto DellaPergola, Roberto Della

Fracchia, LuciaFracchia, Lucia

Garlaschelli, LuigiGarlaschelli, Luigi

Manassero, MarioManassero, Mario

Sansoni, MirellaSansoni, Mirella

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Article abstract of DOI:10.1039/DT9950002763

Addition of triphenylphosphine to the cluster (1-) yielded the derivative (1-), which is stable enough to allow a single-crystal X-ray analysis on the (1+) salt.The cluster contains a triangular metallic framework, the vertices of which are occupied by two Fe(CO)4 groups and one Rh(CO)(PPh3) moiety; the unsaturation of the cluster (46 valence electrons) is brought about by this 16-electron square-planar fragment.The cluster (2-) was obtained by treating with (1-) (molar ratio 1 : 2) in refluxing acetone, and was characterized by infrared spectroscopy and elemental analyses.The adduct >(1-) was prepared by stoichiometric addition of in acetone and the crystal structure of the (1+) salt was elucidated by X-ray analysis.The cluster contains a trigonal-bipyramidal arrangement of metal atoms, with one Au(PPh3) and one Fe(CO)3 group occupying the apical positions.The vertices of the FeRh2 equatorial plane are bound to two terminal carbonyl ligands, and the edges are spanned by three bridging carbonyls.The 31P NMR spectral data for (1-) and >(1-) are consistent with the solid-state structures, but do not exclude the presence of fluxional processes in solution.

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