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, Alexander 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: 2016-04-07T16:14:29Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-07T16:14:29Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015-04-20
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.1021/acs.inorgchem.5b00253
metadata.lang: -
metadata.name: dc.identifier.citation
metadata.value: Inorg. Chem. 2015, 54, 4039−4046
metadata.lang: en_GB
metadata.name: dc.identifier.issn
metadata.value: 10.1021/acs.inorgchem.5b00253
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1930
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: Treatment of the aromatic nitrile complexes trans-[PtCl2(RC6H4CN)2] (R = p-CF3 NC1, H NC2, o-Cl NC3) with the aryl amidoximes p-R'C6H4C(NH2)=NOH (R' = Me AO1, H AO2, Br AO3, CF3 AO4, NO2 AO5) 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}] (1-15; 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 1-16 were characterized by elemental analyses (C, H, N), high-resolution ESI(+)-MS, FTIR, and (1)H NMR techniques, whereas unstable 17 was characterized by HRESI(+)-MS and FTIR. In addition, 8·C4H8O2, 12, and 16·CHCl3 were studied by single-crystal X-ray diffraction.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
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
resources.filename: file.txt
resources.url: https://dspace.spbu.ru/bitstream/11701/1930/1/file.txt
resources.format: Text
resources.size: 4 B