hazel_Gav_Dalton_pincers_2015.pdf (1.7 MB)
The nature of the bonding in symmetrical pincer palladacycles
journal contribution
posted on 2023-06-08, 20:40 authored by Sarote Boonseng, Gavin W Roffe, John SpencerJohn Spencer, Hazel CoxHazel CoxThe accuracy of DFT-optimised geometries of the symmetrical pincer palladacycles PdNCN and PdSCS, [ClPd{2,6- Me2NCH2)2C6H3}] and [ClPd{2,6-(MeSCH2)2C6H3}] respectively, has been evaluated by investigating the performance of eight commonly used density functionals with four combinations of basis set, in reproducing their X-ray crystal structures. It was found that whilst the ?B97XD functional performed best over all, the PBE and TPSS functionals performed best when considering the palladium coordination geometry. The role of the donor atom in the stability and reactivity of the symmetric palladacycles, PdYCY, Y = N, S, or P, has been determined using Bader’s Atoms in Molecules method to elucidate the nature of the bonding, and using a model formation reaction, which involves the C–H activation of the pincer ligand YCY by PdCl2. The calculations reveal distinct differences in the bond strength and nature of the interaction of Pd with the donor atoms Y, which support differences in the thermodynamic stability of the palladacycles.
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Publication status
- Published
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- Published version
Journal
Dalton TransactionsISSN
1477-9226Publisher
Royal Society of ChemistryExternal DOI
Volume
44Page range
7570-7577Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2015-05-04First Open Access (FOA) Date
2015-05-04First Compliant Deposit (FCD) Date
2015-04-29Usage metrics
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