trans-cis C-Pd-C rearrangement in hemichelates

Kinetically unstable heteroleptic trans-bispalladacycles were isolated by using hemichelation. Three structures of trans isomers and five of cis isomers were characterized by X-ray diffraction analysis. The ready trans-to-cis isomerization of such hemichelates that was monitored by variable temperat...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2017, Vol.46 (25), p.8125-8137
Main Authors: Werlé, Christophe, Dohm, Sebastian, Bailly, Corinne, Karmazin, Lydia, Ricard, Louis, Sieffert, Nicolas, Pfeffer, Michel, Hansen, Andreas, Grimme, Stefan, Djukic, Jean-Pierre
Format: Article
Language:English
Subjects:
Chelates
Chemical Sciences
Density functional theory
Isomerization
Isomers
Mathematical analysis
Monitoring
Other
Preserves
X ray diffraction
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Summary:Kinetically unstable heteroleptic trans-bispalladacycles were isolated by using hemichelation. Three structures of trans isomers and five of cis isomers were characterized by X-ray diffraction analysis. The ready trans-to-cis isomerization of such hemichelates that was monitored by variable temperature NMR experiments is facilitated dynamically because the Pd(ii) center can preserve its square planar coordination in a rather low lying transition state, which was localized by methods of the density functional theory. This process is not achievable in the isomerization of conventional homoleptic trans-bispalladacycles since it involves the preliminary partial chelate decoordination and an unfavorable high-lying planar trigonal coordinated - or Y-shaped-Pd(ii) transition state according to DFT investigations.
ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt00872d