Lindqvist-Reis, Patric
- Forschungszentrum Karlsruhe
Abstract
The strongly hydrogen bonded species (CH3)(2)SO center dot center dot center dot H3O+ formed in concentrated hydrochloric acid displays a new low energy feature in its sulfur K-edge X-ray absorption near edge structure (XANES) spectrum. Density Functional Theory-Transition Potential (DFT-TP) calculations reveal that the strong hydrogen bonding decreases the energy of the transition S(1s) -> LUMO, which has antibonding sigma*(S-O) character, with about 0.8 eV. Normal coordinate force. field analyses of the vibrational spectra show that the SO stretching force constant decreases from 4.72 N cm(-1) in neat liquid dimethyl sulfoxide to 3.73 N cm(-1) for the hydrogen bonded (CH3)(2)SO center dot center dot center dot H3O+ species. The effects of sulfur coordination on the ambidentate dimethyl sulfoxide molecule were investigated for the trans-Pd((CH3)(2)SO)(2)Cl-2, trans-Pd((CD3)(2)SO)(2)Cl-2 and cis-Pt((CH3)(2)SO)(2)Cl-2 complexes with square planar coordination of the chlorine and sulfur atoms. The XANES spectra again showed shifts toward low energy for the transition S(1 s) -> LUMO, now with antibonding sigma*(M-Cl, M-S) character, with a larger shift for M = Pt than Pd. DFT-TP calculations indicated that the differences between the XANES spectra of the geometrical cis and trans isomers of the M((CH3)(2)SO)(2)Cl-2 complexes are expected to be too small to allow experimental distinction. The vibrational spectra of the palladium(II) and platinum(II) complexes were recorded and complete assignments of the fundamentals were achieved. Even though the M-S bond distances are quite similar the high covalency especially of the Pt-S bonds induces significant increases in the S-O stretching force constants, 6.79 and 7.18 N cm(-1), respectively.
Published in
Dalton Transactions
2009, number: 8, pages: 1328-1338
Publisher: ROYAL SOC CHEMISTRY
SLU Authors
UKÄ Subject classification
Theoretical Chemistry
Inorganic Chemistry
Physical Chemistry
Publication identifier
- DOI: https://doi.org/10.1039/b814252a
Permanent link to this page (URI)
https://res.slu.se/id/publ/95512