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Reactions of m-chloroperoxybenzoic acid with dimeric cyclopalladated complexes derived from 2-phenyl-2-oxazolines

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Abstract

Cyclopalladated complexes (CPCs) (S,S)-di-μ-Cl(κ2-C,N)2Pd2 (1a,b) and (S,S)-di-μ-OAc(κ2-C,N)2Pd2 (7a,b) obtained from (S)-4-t-butyl-(a) and (S)-4-ethyl-2-phenyl-2-oxazoline (b) were reacted with m-chloroperoxybenzoic acid (m-CPBA) at room temperature in methylene chloride, ethyl acetate or acetonitrile followed by workup with lithium chloride. Oxidation products formed in these reactions include dinuclear complexes (S,S)-di-μ-Cl(κ2-N,O)2Pd2 (2a), (S,S)-di-μ-oxo(κ2-N,O)2Pd2Cl2 (2b), and (S,S)-di-μ-(m-Cl-C6H4CO2)(κ2-N,O)2Pd2 (3a,b), mononuclear derivatives (S,S)-bis(κ2-N,O)Pd (4a,b) and dinuclear monooxidation complexes (S,S)-di-μ-Cl(κ2-N,O)(κ2-C,N)Pd2 (5a,b). Each complex was isolated in low yield (6–46 %) with the combined yield of oxidation products reaching up to 64 %. The best selectivity in product distribution was observed for the reactions of μ-OAc–CPCs 7a,b with 2.7 equiv. of m-CPBA in acetonitrile, in which oxygen-insertion adducts 2a and 4b were isolated in 44 and 46 % yields, respectively. The structures of all complexes were supported by spectroscopic methods. An X-ray crystallographic study of compound 4a was performed, confirming its mononuclear structure and revealing an unusual bent geometry.

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Acknowledgments

The authors would like to thank the University of North Dakota for financial support. The authors are also grateful to Benjamin E. Kucera, Victor G. Young, Jr., and the X-ray Crystallographic Laboratory in the Department of Chemistry, University of Minnesota, for the X-ray crystal structure of complex 4a.

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Author notes

  1. Kristopher J. Keuseman

    Present address: Department of Natural and Applied Sciences, Mount Mercy University, Cedar Rapids, IA, 52402-4797, USA

Authors and Affiliations

  1. Department of Chemistry, University of North Dakota, Grand Forks, ND, 58202-9024, USA

    Jonathan E. Kukowski, Kristopher J. Keuseman & Irina P. Smoliakova

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  1. Jonathan E. Kukowski
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Correspondence to Irina P. Smoliakova.

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Kukowski, J.E., Keuseman, K.J. & Smoliakova, I.P. Reactions of m-chloroperoxybenzoic acid with dimeric cyclopalladated complexes derived from 2-phenyl-2-oxazolines. Transition Met Chem 40, 877–889 (2015). https://doi.org/10.1007/s11243-015-9984-4

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