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Reactions of nitrosoarenes containing electron-withdrawing substituents with coordinated CO. Synthesis and structure of complexes Pd2(OAc)2(p-ClC6H4N[p-ClC6H3NO])2 and Pd2(OAc)2(o-ClC6H4N[o-ClC6H3NO])2

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Abstract

The reaction of tetranuclear Pd4(μ-COOCH3)4(μ-CO)4 cluster (1a) with p- and o-chloronitrosobenzenes was found to give dinuclear nitrosoamide complexes, Pd2(OAc)2(p-ClC6H4N[p-ClC6H3NO])2 (4) and Pd2(OAc)2(o-ClC6H4N[o-ClC6H3NO])2 (5), respectively. The formation of complexes 4 and 5 is accompanied by evolution of CO2, resulting from oxidation of CO coordinated in cluster 1. Complexes 4 and 5 were characterized by elemental analysis and IR and 1H NMR spectroscopy; their structures were studied by EXAFS. The reactions of dinuclear complex 4 with molecular hydrogen and CO were studied. The major products of reduction of 4 with hydrogen include metallic palladium, acetic acid, cyclohexanone, and molecular nitrogen. Treatment of complex 4 with CO under mild conditions (1 atm, 20 °C) affords p-chlorophenyl isocyanate.

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Authors and Affiliations

  1. N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky prosp., 119991, Moscow, Russian Federation

    S. T. Orlova, T. A. Stromnova, D. N. Kazyul"kin & L. I. Boganova

  2. G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 5 prosp. Akad. Lavrent"eva, 630090 Novosibirsk, Russian Federation

    D. I. Kochubey & B. N. Novgorodov

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  1. S. T. Orlova
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  2. T. A. Stromnova
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  3. D. N. Kazyul"kin
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  4. L. I. Boganova
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  5. D. I. Kochubey
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  6. B. N. Novgorodov
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Orlova, S.T., Stromnova, T.A., Kazyul"kin, D.N. et al. Reactions of nitrosoarenes containing electron-withdrawing substituents with coordinated CO. Synthesis and structure of complexes Pd2(OAc)2(p-ClC6H4N[p-ClC6H3NO])2 and Pd2(OAc)2(o-ClC6H4N[o-ClC6H3NO])2 . Russian Chemical Bulletin 53, 819–824 (2004). https://doi.org/10.1023/B:RUCB.0000037849.06365.7f

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