Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/16501
Title: Reactions of hydrotris(pyrazolyl)borate (Tp)-supported ruthenium dihydrogen complexes [TpRu(L2)(H2)]+ (L2 = dppm, dppp, (PPh3)2) with O2
Authors: Man, ML
Zhu, J
Ng, SM
Zhou, Z
Yin, C
Lin, Z
Lau, CP
Issue Date: 2004
Publisher: American Chemical Society
Source: Organometallics, 2004, v. 23, no. 26, p. 6214-6220 How to cite?
Journal: Organometallics 
Abstract: The η2-dihydrogen complex [TpRu(L3)(H 2)]+ (L2 = dppm, dppp, or (PPh 3)2) prepared in situ by protonation of the hydride precursor reacts with O2 to yield the paramagnetic Ru III-superoxo complex [TpRuIII(L2)(O 2)]+, in which antiferromagnetic coupling between the RuIIIion (d5, S = 1/2) and the coordinated Superoxide radical (S = 1/2) does not seem to be present. In THF, the superoxo moiety of the complex readily abstracts a hydrogen atom from the solvent to generate the hydroperoxo (-OOH-) group, which then changes into the hydroxo ligand by transferring an oxygen atom to a phosphine ligand. Density functional theory calculation at the B3LYP level on the model complex [TpRu(PH3) 2(O2)]+ shows that the RuIII- superoxo(O2 -) structure with a triplet state is more stable than the RuIV-peroxo(O2 2-) structure with a singlet state by 5.2 kcal/mol. On the other hand, the analogous Cp model complex [CpRu(PH3)2(O2)]+ prefers the RuIV-peroxo(O2 2-) structure over the RuIII-superoxo-(O2 -) structure by 2.9 kcal/mol.
URI: http://hdl.handle.net/10397/16501
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om049403o
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