Photochemical reductive elimination of [PtIV(NH3)4(NH2)Cl]2+: Photogeneration of hydrazine

When [PtIV(NH3)5Cl]3+ is deprotonated the complex [PtIV(NH3)4(NH2)Cl]2+ is formed. Upon NH2−→PtIV LMCT excitation (λirr>250nm) a reductive elimination takes place: [PtIV(NH3)4(NH2)Cl]2+→[PtII(NH3)3Cl]++N2H4+H+. Since Pt(II) ammine complexes can be reoxidized to Pt(IV) by H2O2 it is suggested that...

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Bibliographic Details
Published in:Inorganic chemistry communications 2013-03, Vol.29, p.53-55
Main Authors: Kunkely, Horst, Vogler, Arnd
Format: Article
Language:English
Subjects:
Coordination chemistry
Hydrazine
Photochemistry
Platinum
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Summary:When [PtIV(NH3)5Cl]3+ is deprotonated the complex [PtIV(NH3)4(NH2)Cl]2+ is formed. Upon NH2−→PtIV LMCT excitation (λirr>250nm) a reductive elimination takes place: [PtIV(NH3)4(NH2)Cl]2+→[PtII(NH3)3Cl]++N2H4+H+. Since Pt(II) ammine complexes can be reoxidized to Pt(IV) by H2O2 it is suggested that in a cyclic process the overall reaction could proceed according to the equation: 2 NH3+H2O2→N2H4+2 H2O. [Display omitted] ► The complex [PtIV(NH3)4(NH2)Cl]2+ shows an (amide to PtIV) LMCT absorption. ► Upon LMCT excitation a reductive elimination occurs. ► The photolysis yields [PtII(NH3)3Cl]+ and hydrazine.
ISSN:1387-7003
1879-0259
DOI:10.1016/j.inoche.2012.12.007