Features of reactions of α-substituted acetylacetonate complexes

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The reactions of coordinated ligands in acetylacetonate complexes of chromium and boron difluoride were studied by chromatograph mass spectrometry. It was found that bromo- and thiophenyl-substituted acetylacetonates of boron difluoride, unlike chromium complexes, do not interact with thiophenol. The interaction of thio-substituted chelates with SO2Cl2 also occurs differently. For chromium complexes, the reaction is accompanied by the replacement of the thioalkyl or thioaryl substituent by a chlorine atom. Thioethyl-substituted acetylacetonate of boron difluoride reacts with SO2Cl2 like aromatic analogues with chlorination of the ethyl group. Thioaryl-substituted acetylacetonate of boron difluoride does not react with SO2Cl2. In addition, it was found that bromo- and thiosubstituted chromium acetylacetonates react with sulfenyl chlorides with the replacement of the α-substituent by a chlorine atom. It was suggested that the difference in the reactivity of chromium acetylacetonates and boron difluoride is due to different charge distributions in the chelate cycle. The significant electroacceptor character of the BF2 group leads to the appearance of a positive charge on the substituent associated with the chelate cycle of the boron complexes.

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I. Svistunova

Far Eastern Federal University, Institute of Science-Intensive Technologies

编辑信件的主要联系方式.
Email: svistunova.iv@dvfu.ru
俄罗斯联邦, Vladivostok

G. Tretyakova

Far Eastern Federal University, Institute of Science-Intensive Technologies

Email: svistunova.iv@dvfu.ru
俄罗斯联邦, Vladivostok

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3. Fig. 1. Scheme of interaction of F2B(acacSCN) (II) with thiophenol.

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4. Fig. 2. Proposed scheme of interaction of halogen- and RS-substituted metal acetylacetonates with thiols.

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5. Fig. 3. Scheme of interaction of RS-substituted metal acetylacetonates with sulfuryl chloride.

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6. Fig. 4. Scheme of interaction of thioethyl-substituted acetylacetonates of boron difluoride with sulfuryl chloride.

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7. Fig. 5. Scheme of interaction of Cr(acacSPh)3 and Cr(acacSEt)3 with sulfenyl chloride.

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8. Fig. 6. Interaction of Cr(acacBr)3 with sulfenyl chloride.

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