Metal and ligand K-edge XAS of titanium-TEMPO complexes: Determination of oxidation states and insights into Ti-O bond homolysis

Inorganic Chemistry

Volumn 45, Issue 11, 2006, Pages 4468-4477

  George, Serena DeBeer ^a   Huang, Kuo Wei ^b   Waymouth, Robert M ^b   Solomon, Edward I ^a,b  

^a SLAC NATIONAL ACCELERATOR LABORATORY   (United States)

^b STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE OXIDE; LIGAND; METAL; POTASSIUM; TEMPO; TITANIUM;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; ELECTRON; OXIDATION REDUCTION REACTION; SPECTROMETRY;

CYCLIC N-OXIDES; ELECTRONS; LIGANDS; METALS; MODELS, MOLECULAR; OXIDATION-REDUCTION; POTASSIUM; SPECTROMETRY, X-RAY EMISSION; TITANIUM;

EID: 33745711779     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic060402t     Document Type: Article

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36. 2 series (37%, 32%, and 25% per Ti-Cl bond, respectively). This reflects the increased donation of TEMPO relative to chloride.
37. 2ClTEMPO give similar results, ref 8.
38. This is most likely due to the use of the BP86 functional in this case vs the use of B3LYP/6-31G in ref 8. The hybrid functional will generally result in less covalent bonding and thus lower energies.
39. + shows that the total Ti-Cp character increases from 51% to 55%.