Understanding the exceptional hydrogen-atom donor characteristics of water in Ti(III)-mediated free-radical chemistry.
In recent years solid evidence of HAT reactions involving water as hydrogen atom source have been presented. In this work we demonstrate that the efficiency of titanocene(III) aqua complexes as an unique class of HAT reagents is based on two key features: (a) excellent binding capabilities of water toward titanocene(III) complexes and (b) a low activation energy for the HAT step. The theory has predictive capabilities fitting well with the experimental results and may aid to find more examples of this remarkable radical reaction.
Paradas
Miguel
M
Department of Organic Chemistry, Faculty of Sciences, University of Granada, Campus Fuentenueva s/n, E-18071 Granada, Spain.
Campaña
Araceli G
AG
Jiménez
Tania
T
Robles
Rafael
R
Oltra
J Enrique
JE
Buñuel
Elena
E
Justicia
José
J
Cárdenas
Diego J
DJ
Cuerva
Juan M
JM
D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D005609:Free Radicals; D009942:Organometallic Compounds; D014867:Water; C406884:titanocene; D006859:Hydrogen