Roukala, Juho, Orr, Simon T., Hanna, John V., Vaara, Juha, Ivanov, Alexander V., Antzutkin, Oleg N. and Lantto, Perttu (2016) Experimental and first-principles NMR analysis of Pt(II) complexes with O,O′-Dialkyldithiophosphate ligands. The Journal of Physical Chemistry A, 120 (42). pp. 8326-8338. doi:10.1021/acs.jpca.6b09586 ISSN 1089-5639.
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Abstract
Polycrystalline bis(dialkyldithiophosphato)Pt(II) complexes of the form [Pt{S2P(OR)2}2] (R = ethyl, iso-propyl, iso-butyl, sec-butyl or cyclo-hexyl group) were studied using solid-state 31P and 195Pt NMR spectroscopy, to determine the influence of R to the structure of the central chromophore. The measured anisotropic chemical shift (CS) parameters for 31P and 195Pt afford more detailed chemical and structural information, as compared to isotropic CS and J couplings alone. Advanced theoretical modeling at the hybrid DFT level, including both crystal lattice and the important relativistic spin–orbit effects qualitatively reproduced the measured CS tensors, supported the experimental analysis, and provided extensive orientational information. A particular correction model for the non-negligible lattice effects was adopted, allowing one to avoid a severe deterioration of the 195Pt anisotropic parameters due to the high requirements posed on the pseudopotential quality in such calculations. Though negligible differences were found between the 195Pt CS tensors with different substituents R, the 31P CS parameters differed significantly between the complexes, implying the potential to distinguish between them. The presented approach enables good resolution and a detailed analysis of heavy-element compounds by solid-state NMR, thus widening the understanding of such systems.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics |
| Library of Congress Subject Headings (LCSH): | Coordination compounds -- Magnetic properties, Nuclear magnetic resonance spectroscopy |
| Journal or Publication Title: | The Journal of Physical Chemistry A |
| Publisher: | American Chemical Society |
| ISSN: | 1089-5639 |
| Official Date: | 30 September 2016 |
| Dates: | Date Event 30 September 2016 Available 30 September 2016 Accepted 22 September 2016 Submitted |
| Volume: | 120 |
| Number: | 42 |
| Page Range: | pp. 8326-8338 |
| DOI: | 10.1021/acs.jpca.6b09586 |
| Status: | Peer Reviewed |
| Publication Status: | Published |
| Access rights to Published version: | Restricted or Subscription Access |
| Date of first compliant deposit: | 23 January 2017 |
| Date of first compliant Open Access: | 28 September 2017 |
| Funder: | Suomen Kulttuurirahasto [Finnish Cultural Foundation], Jyväskylän yliopisto, Tauno Tönningin Säätiö [Tauno Tönningin Foundation], Oulun yliopisto [University of Oulu], Suomen Akatemia [Academy of Finland], Engineering and Physical Sciences Research Council (EPSRC), Advantage West Midlands (AWM), European Regional Development Fund (ERDF) |
| Grant number: | 125316, 218191, 255641, 28566, 258565 (Suomen Akatemia) |
| URI: | https://wrap.warwick.ac.uk/84124/ |
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