title: Bifunctional reactivity of amidoximes observed upon nucleophilic addition to metal-activated nitriles
metadata.name: dc.contributor.author
metadata.value: Bolotin, Dmitrii S.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Demakova, Marina Ya.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Novikov, Aleksander S.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Avdontceva, Margarita S.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kuznetsov, Maxim L.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Bokach, Nadezhda A.
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kukushkin, Vadim Yu.
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-16T03:15:13Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-16T03:15:13Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 0020-1669
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/2111
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: Treatment of the aromatic nitrile complexes trans-[PtCl2(RC6H4CN)2] (R = p-CF3 1, H 2, o-Cl 3) with the aryl amidoximes p-R’C6H4C(NH2)=NOH (R’ = Me 4, H 5, Br 6, CF3 7, NO2 8) in all combinations, followed by addition of 1 equiv of AgOTf and then 5 equiv of Et3N leads to the chelates [PtCl{HN=C(RC6H4)ON=C(C6H4R’-p)NC(RC6H4)=NH}] (9–23; 15 examples; yields 71–88% after column chromatography) derived from the platinum(II)-mediated coupling between metal-activated nitriles and amidoximes. The mechanism of this reaction was studied experimentally by trapping and identification of the reaction intermediates and it was also investigated theoretically at the DFT level of theory. The combined experimental and theoretical results indicate that the coupling with the nitrile ligands involves both the HON and monodeprotonated NH2 groups of the amidoximes, whereas in the absence of the base, the NH2 functionality is inactive toward the coupling. The observed reaction represents the first example of bifunctional nucleophilic behavior of amidoximes. The complexes 9–24 were characterized by elemental analyses (C, H, N), high resolution ESI+-MS, FTIR, 1H NMR techniques, whereas unstable 25 was characterized by HRESI+-MS and FTIR. In addition, 16•C4H8O2, 20, and 24•CHCl3 were studied by single-crystal X-ray diffraction.
metadata.lang: en_GB
metadata.name: dc.publisher
metadata.value: ACS
metadata.lang: en_GB
metadata.name: dc.relation.ispartofseries
metadata.value: Inorganic Chemistry;vol. 54
metadata.lang: -
metadata.name: dc.subject
metadata.value: nucleophilic addition
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: nitriles
metadata.lang: en_GB
metadata.name: dc.subject
metadata.value: ligand reactivity
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Bifunctional reactivity of amidoximes observed upon nucleophilic addition to metal-activated nitriles
metadata.lang: en_GB
metadata.name: dc.type
metadata.value: Article
metadata.lang: en_GB
resources.filename: Graphical Abstracts.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/2111/1/Graphical%20Abstracts.pdf
resources.format: Adobe PDF
resources.size: 360,85 kB