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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

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Tartalom: http://pubs.rsc.org/en/Content/ArticleLanding/2009/DT/b81...
Archívum: MTA Könyvtár
Gyűjtemény: Status = Published



Type = Article
Cím:
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
Létrehozó:
Risberg, Emiliana Damian
Mink, János
Abbasi, Alireza
Hajba, László
Bencze, Éva
Dátum:
2009
Téma:
QD Chemistry / kémia
QD03 Inorganic chemistry / szervetlen kémia
TK Electrical engineering. Electronics Nuclear engineering / elektrotechnika, elektronika, atomtechnika
Tartalmi leírás:
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.
Típus:
Article
PeerReviewed
Formátum:
text
Azonosító:
Risberg, Emiliana Damian and Mink, János and Abbasi, Alireza and Hajba, László and Bencze, Éva (2009) 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. DALTON TRANSACTIONS (8). pp. 1328-1338. ISSN 1477-9226
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