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Reduction of Nitric Oxide by Tetramesityliridium(IV) and Cobaltocene. Reactions of Hyponitrite Complexes and of the Ether 5-C5H5)(η4-C5H5)>(μ-O-exo) with Nitroalkanes, Acids and Amines

DOI: 10.1039/DT9940002223

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2223 - 2232 (1994)

Update date:2022-08-04

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Authors:

Hay-Motherwell, Robyn S.Hay-Motherwell, Robyn S.

Wilkinson, GeoffreyWilkinson, Geoffrey

Sweet, Tracy K. N.Sweet, Tracy K. N.

Hursthouse, Michael B.Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9940002223

The interactions of either Ir(mes)4 (mes = C6H2Me3-2,4,6) or Co(cp)2 (cp = η5-C5H5) with NO in light petroleum gave unstable solids the IR spectra of which allow them to be formulated as hyponitrite complexes, e.g. 2(N2O2) 1; their reaction with MeNO2 is described.The compound Co(cp)2 with either NO or Ag2N2O2 in toluene gave N2O and the very reactive ether 4-C5H5)>2(μ-O-exo) 2.This reacts with nitroalkanes where the product depends on the nature of the nitroalkane.Nitromethane produced both Co(cp)2(1+)CH2=NO2(1-)*H2O 3 and 4-C5H5)>2<(μ-CH(NO2)-exo> 4, while Me2CH(NO2) gave Co(cp)<η4-C5H5(CMe2NO2)-exo> and EtNO2 corresponding species to 3 and 4 (i.e. 6 and 7).Reactions of 2 with alcohols or phenylacetylene gave mononuclear species of the same type as 4; treatment with NH2Ph or NHPh2 also gave similar exo complexes 8 and 9 respectively.All these exo species reacted with CHCl3 to give the exo-CCl3 compound by facile C-C bond cleavage.Mechanisms for the various reactions are discussed.The structures of compounds 2-4, 8 and 9 have been confirmed by X-ray crystallography: 2 and 4 contain Co(cp)(η4-C5H5) moieties bridged by oxygen or CH(NO2) groups while 8 and 9 are monomers with exo-NHPh or -NPh2 groups.In all cases but one (2) there are near-eclipsed C5CoC5 geometries; for one of the cobalts in 2 there is a twist of ca. 16 deg from the eclipsed configuration.Compound 3 has Co(cp)2(1+) and CH2NO2(1-) ions the latter being involved in strong hydrogen bonding with the H2O molecule also present in the lattice.In both 8 and 9 there is structural evidence for ? interaction between p lone pairs on the planar nitrogen atom and the ? system of a phenyl ring.

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Product name:Co(cp)[η-4-C5H5-(NHPh)-exo]

Cas No:158369-42-7

158369-42-7

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