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Title

Reactions of an osmium-hexahydride complex with cytosine, deoxycytidine, and cytidine: The importance of the minor tautomers

AuthorsEsteruelas, Miguel A. ; García-Raboso, Jorge ; Oliván, Montserrat
Issue Date2012
PublisherAmerican Chemical Society
CitationInorganic Chemistry 51(17): 9522-9528 (2012)
AbstractComplex OsH 6(P iPr 3) 2 (1) deprotonates cytosine to give molecular hydrogen and the d 4- trihydride derivative OsH 3(cytosinate)(P iPr 3) 2 (2), which in solution exists as a mixture of isomers containing κ 2-N1,O (2a) and κ 2-N3,O (2b) amino-oxo and κ 2-N3,N4 (2c) imino-oxo tautomers. The major isomer 2b associates with the minor one 2c through N-H⋯N and N-H⋯O hydrogen bonds to form [2b·2c] 2 dimers, which crystallize from saturated pentane solutions of 2. Complex 1 is also able to perform the double deprotonation of cytosine (cytosinate′) to afford the dinuclear derivative (P iPr 3) 2H 3Os(cytosinate′)OsH 3(P iPr 3) 2 (3), where the anion is coordinated κ 2-N1,O and κ 2-N3,N4 to two different OsH 3(P iPr 3) 2 metal fragments. The deprotonation of deoxycytidine and cytidine leads to OsH 3(deoxycytidinate)(P iPr 3) 2 (4) and OsH 3(cytidinate)(P iPr 3) 2 (5), respectively, containing the anion κ 2-N3,N4 coordinated. Dimer [2b·2c] 2 and dinuclear complex 3 have been characterized by X-ray diffraction analysis. © 2012 American Chemical Society.
URIhttp://hdl.handle.net/10261/64947
DOI10.1021/ic3013238
Identifiersdoi: 10.1021/ic3013238
issn: 0020-1669
e-issn: 1520-510X
Appears in Collections:(ISQCH) Artículos
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