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Reduction of nitric-oxide by tetramesityliridium(iv) and cobaltocene - reactions of hyponitrite complexes and of the ether [co(eta(5)-c5h5)(eta(4)-c5h5)](mu-o-exo) with nitroalkanes, acids and amines

Haymotherwell, R. S., Wilkinson, Geoffrey, Sweet, Tracy and Hursthouse, Michael B. 1994. Reduction of nitric-oxide by tetramesityliridium(iv) and cobaltocene - reactions of hyponitrite complexes and of the ether [co(eta(5)-c5h5)(eta(4)-c5h5)](mu-o-exo) with nitroalkanes, acids and amines. Journalof The Chemical Society-Dalton Transactions (15) , pp. 2223-2232.

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Abstract

The interactions of either Ir(mes)4 (mes = C6H2Me3-2,4,6) or Co(cp)2 (cp = eta5-C5H5) with NO in light petroleum gave unstable solids the IR spectra of which allow them to be formulated as hyponitrite complexes, e.g. [Co(cp)2]2(N2O2) 1; their reaction with MeNO2 is described. The compound Co(cp)2 with either NO or Ag2NO2 in toluene gave N2O and the very reactive ether [Co(cp)(eta4-C5H5)]2(mu-O-exo) 2. This reacts with nitroalkanes where the product depends on the nature of the nitroalkane. Nitromethane produced both Co(cp)2+ CH2=NO2-.H2O 3 and [Co(cp)(eta4-C5H5)]2[(mu-CH(NO2)-exo] 4, while Me2CH(NO2) gave Co(cp)[eta4-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 structuresof compounds 2-4, 8 and 9 have been confirmed by X-ray crystallography: 2 and 4 contain Co(cp) (eta4-C5H5) moieties bridged by oxygen or CH(NO2) groups while 8 and 9 are monomers with exo-NHPh or -NPh2 groups. In all cases butone (2) there are near-eclipsed C5CoC5 geometries; for one of the cobalts in 2 there is a twist of ca. 16-degrees from the eclipsed configuration. Compound 3 has Co(CP)2+ and CH2NO2- 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 pi interaction between p lone pairs on the planar nitrogen atom and the pi system of a phenyl ring.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Engineering
Subjects: Q Science > QD Chemistry
Last Modified: 08 May 2019 02:40
URI: http://orca.cf.ac.uk/id/eprint/43891

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