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http://hdl.handle.net/11701/1937
Полная запись метаданных
Поле DC | Значение | Язык |
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dc.contributor.author | Kinzhalov, MA | - |
dc.contributor.author | Novikov, AS | - |
dc.contributor.author | Luzyanin, KV | - |
dc.contributor.author | Haukka, M | - |
dc.contributor.author | Pombeiro, AJL | - |
dc.contributor.author | Kukushkin, VY | - |
dc.date.accessioned | 2016-04-07T16:43:25Z | - |
dc.date.available | 2016-04-07T16:43:25Z | - |
dc.date.issued | 2016 | - |
dc.identifier.citation | New J. Chem., 2016, 40, 521 | en_GB |
dc.identifier.uri | http://hdl.handle.net/11701/1937 | - |
dc.description.abstract | Reaction between equimolar amounts of trans-[PdC(PPh3)(2)(CNR)][BF4] (R = t-Bu 1, Xyl 2) and diisopropylammonium azide 3 gives the tetrazolate trans-[PdCl(PPh3)(2)(CN(4)t-Bu)] (67%, 4) or trans-[PdCl(PPh3)(2)(CN(4)Xyl)] (72%, 5) complexes. 4 and 5 were characterized by elemental analyses (C, H, N), HRES1(+)-MS, H-1 and C-13{H-1} NMR spectroscopies. In addition, the structure of 4 was elucidated by a single-crystal X-ray diffraction. DFT calculations showed that the mechanism for the formal cycloaddition (CA) of N-3(-) to trans-[PdCl(PH3)(2)(CNMe)](+) is stepwise. The process is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN-intermediate. The second step of the formal CA, i.e. cyclization, is rate Limiting. Despite the fact that the substitution of CNMe by the N-3(-) Ligand is slightly thermodynamically favorable, we were unable to find paths on the potential energy surface for hypothetical CA between uncomplexed isocyanide and palladium-bound azide. Thus, we believe that the experimentally observed palladium tetrazolate complexes are, in fact, generated from the negatively charged uncomplexed azide and the positively charged metal-bound isocyanide species, and this reaction path is favorable from the viewpoint of Coulomb attraction. | en_GB |
dc.title | PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide | 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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