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http://hdl.handle.net/11701/1929
Полная запись метаданных
Поле DC | Значение | Язык |
---|---|---|
dc.contributor.author | Andrusenko, EV | - |
dc.contributor.author | Kabin, EV | - |
dc.contributor.author | Novikov, AS | - |
dc.contributor.author | Bokach, NA | - |
dc.contributor.author | Starova, GL | - |
dc.contributor.author | Zolotarev, AA | - |
dc.contributor.author | Kukushkin, VY | - |
dc.date.accessioned | 2016-04-07T16:12:38Z | - |
dc.date.available | 2016-04-07T16:12:38Z | - |
dc.date.issued | 2015 | - |
dc.identifier.citation | Eur. J. Inorg. Chem. 2015, 4894–4904 | en_GB |
dc.identifier.uri | http://hdl.handle.net/11701/1929 | - |
dc.description.abstract | 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. | en_GB |
dc.description.abstract | 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. | en_GB |
dc.title | Highly Reactive Ni-II-Bound Nitrile-Oxime Coupling Intermediates | en_GB |
Располагается в коллекциях: | Research Reports |
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Файл | Описание | Размер | Формат | |
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file.txt | 4 B | Text | Просмотреть/Открыть |
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