Ambidentate coordination in hydrogen bonded dimethyl sulfoxide, (CH3)2SO⋯H3O+, and in dichlorobis(dimethyl sulfoxide) palladium(ii) and platinum(ii) solid solvates, by vibrational and sulfur K-edge X-ray absorption spectroscopy

Emiliana Damian Risberg, János Mink, Alireza Abbasi, Mikhail Yu Skripkin, Laszló Hajba, Patric Lindqvist-Reis, Éva Bencze, Magnus Sandström

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The strongly hydrogen bonded species (CH3)2SO⋯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 σ*(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)2SO⋯H3O+ species. The effects of sulfur coordination on the ambidentate dimethyl sulfoxide molecule were investigated for the trans-Pd((CH3)2SO)2Cl2, trans-Pd((CD3)2SO)2Cl2 and cis-Pt((CH3)2SO)2Cl2 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 σ*(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)2SO)2Cl2 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.

Original languageEnglish
Pages (from-to)1328-1338
Number of pages11
JournalJournal of the Chemical Society. Dalton Transactions
Issue number8
DOIs
Publication statusPublished - Feb 10 2009

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Ambidentate coordination in hydrogen bonded dimethyl sulfoxide, (CH<sub>3</sub>)<sub>2</sub>SO⋯H<sub>3</sub>O<sup>+</sup>, and in dichlorobis(dimethyl sulfoxide) palladium(ii) and platinum(ii) solid solvates, by vibrational and sulfur K-edge X-ray absorption spectroscopy'. Together they form a unique fingerprint.

  • Cite this