title: Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates
metadata.name: dc.contributor.author
metadata.value: Andrusenko, EV
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kabin, EV
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Novikov, AS
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Bokach, NA
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Starova, GL
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Zolotarev, AA
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kukushkin, VY
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-07T16:12:38Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-07T16:12:38Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015
metadata.lang: -
metadata.name: dc.identifier.citation
metadata.value: Eur. J. Inorg. Chem. 2015, 4894–4904
metadata.lang: en_GB
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1929
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: Nickel(II)-mediated coupling between the cyanamide Me2NCN and the ketoximes Me(R)C=NOH (R = Me, Ph) gives chelates of the general formula [NiClx(H2O)(y){HN=C(NMe2)(ON=C(R)Me)}(2)](n+) ([1](+): R = Me; x = 1, y = 0; salts with both Cl- and [NiCl4](2-) were isolated; [2](2+): R = Me; x = 0, y = 2; salt with Cl- was isolated; [3](+): R = Ph; x = 1, y = 1; salt with Cl- was isolated) and the iminium salts [H2N=C(NMe2)ON=C(R)Me](+) ([4](+): R = Me; salt with [NiCl4](2-) was isolated; [5](+): R = Ph; salt with Cl- was isolated). This reaction demonstrates the difference in the reactivity between conventional nitriles and dialkylcyanamides: whereas nitriles RCN (R = Alk, Ar) react with Ni-II/ketoxime systems to afford (1,3,5-triazapentadiene)Ni-II species, formed by postulated nitrile-oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide-oxime coupling products or the Busch-type complex [Ni{HN=C(Me)CH2C(Me-2)NH2}(2)]Cl-2 ([6]Cl-2). The reason for the different stability of the coupling products was interpreted theoretically on the basis of quantum chemical calculations (M06-L/6-31G* level of theory). The NMe2 moiety in the chelate ligands leads to an increase in electron-density delocalization and also stabilizes the systems in terms of electrostatic factors.
metadata.lang: en_GB
metadata.name: dc.description.abstract
metadata.value: C1 [Andrusenko, Elena V.; Kabin, Evgeniy V.; Novikov, Alexander S.; Bokach, Nadezhda A.; Starova, Galina L.; Zolotarev, Andrey A.; Kukushkin, Vadim Yu.] St Petersburg State Univ, Inst Chem, St Petersburg 198504, Russia.
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates
metadata.lang: en_GB
resources.filename: file.txt
resources.url: https://dspace.spbu.ru/bitstream/11701/1929/1/file.txt
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resources.size: 4 B