Solid-state structure, quantum calculations and spectroscopic characterization of the hydrogen-bonded complex [Os(bpy)2(CO) (EtO⋯H-DMAP)][PF6]2

Claudio Garino, Roberto Gobetto, Carlo Nervi, Luca Salassa, Gianluca Croce, Marco Milanesio, Edward Rosenberg, J. B.Alexander Ross

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

The new H-bonded complex [Os(bpy)2(CO)(EtO⋯H-DMAP)] [PF6]2, where DMAP = 4-(dimethylamino)pyridine and bpy = 2,2′-bipyridine, has been synthesized and characterized by X-ray diffraction, IR, solution and solid-state NMR spectroscopy. The complex shows a strong hydrogen bond between the protonated DMAP moiety and the deprotonated ethanolic group directly bonded to the Os atom. High-speed (28 KHz) solid-state 1H MAS NMR spectroscopy and quantum-mechanical calculations were used to assess the location of the hydrogen atom involved in the H-bond. Both confirmed a proton characteristic of an N-H⋯O-Y hydrogen bond. A molecular orbital analysis was performed to elucidate the IR CO stretching frequency red shift of the H-bonded complex with respect to [Os(bpy) 2(CO)O(H)Et]-[OTf]2. Absorption spectra indicate that the H-bond is present both in water and dichloromethane solutions. However, no direct evidence of the H-bond interaction in solution is observed from the 1H NMR spectrum (CD2Cl2) between 298 and 193 K.

Lingua originaleInglese
pagine (da-a)606-614
Numero di pagine9
RivistaEuropean Journal of Inorganic Chemistry
Numero di pubblicazione3
DOI
Stato di pubblicazionePubblicato - 4 feb 2005

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