title: PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
metadata.name: dc.contributor.author
metadata.value: Kinzhalov, MA
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Novikov, AS
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Luzyanin, KV
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Haukka, M
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Pombeiro, AJL
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kukushkin, VY
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-07T16:43:25Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-07T16:43:25Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2016
metadata.lang: -
metadata.name: dc.identifier.citation
metadata.value: New J. Chem., 2016, 40, 521
metadata.lang: en_GB
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1937
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: 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.
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: PdII-mediated integration of isocyanides and azide ions might proceed via formal 1,3-dipolar cycloaddition between RNC ligands and uncomplexed azide
metadata.lang: en_GB
resources.filename: file.txt
resources.url: https://dspace.spbu.ru/bitstream/11701/1937/1/file.txt
resources.format: Text
resources.size: 4 B