Ligand-Directed Reactivity in Dioxygen and Water Binding to cis -[Pd(NHC) 2 (η 2 -O 2 )]

Palluccio, Taryn D. [Department
of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, United States]; Cai, Xiaochen [Department
of Chemistry, University of Miami, Coral Gables, Florida 33146, United States]; Majumdar, Subhojit [Department
of Chemistry, University of Miami, Coral Gables, Florida 33146, United States]; Serafim, Leonardo F. [Department
of Chemistry, University of Miami, Coral Gables, Florida 33146, United States]; Tomson, Neil C. [Max-Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany; Department
of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States] (ORCID:0000000191311039); Wieghardt, Karl; Cazin, Catherine S. [Department
of Chemistry and Center for Sustainable Chemistry, Ghent University, Campus
Sterre, Building S-3, Krijgslaan 281, Ghent 9000, Belgium]; Nolan, Steven P. [Department
of Chemistry and Center for Sustainable Chemistry, Ghent University, Campus
Sterre, Building S-3, Krijgslaan 281, Ghent 9000, Belgium] (ORCID:0000000190242035); Rybak-Akimova, Elena V. [Department
of Chemistry, Tufts University, 62 Talbot Avenue, Medford, Massachusetts 02155, United States]; Fernández-González, Miguel Ángel [Department
of Analytical Chemistry, Physical Chemistry and Chemical Engineering, Universidad de Alcalá, Madrid 28871, Spain]; Temprado, Manuel [Department
of Analytical Chemistry, Physical Chemistry and Chemical Engineering, Universidad de Alcalá, Madrid 28871, Spain]; Captain, Burjor [Department
of Chemistry, University of Miami, Coral Gables, Florida 33146, United States] (ORCID:0000000272725655); Hoff, Carl D. [Department
of Chemistry, University of Miami, Coral Gables, Florida 33146, United States]

doi:10.1021/jacs.7b09905

We report on spectroscopic measurements on the $4 f^{7} 6 s^{2}^{8} S_{7 / 2}^{\circ<#comment/>} \to<#comment/> 4 f^{7} (^{8} S^{\circ<#comment/>}) 6 s 6 p (^{1} P^{\circ<#comment/>})^{8} P_{9 / 2}$ transition in neutral europium-151 and europium-153 at 459.4 nm. The center of gravity frequencies for the 151 and 153 isotopes, reported for the first time in this paper, to our knowledge, were found to be 652,389,757.16(34) MHz and 652,386,593.2(5) MHz, respectively. The hyperfine coefficients for the $6 s 6 p (^{1} P^{\circ<#comment/>})^{8} P_{9 / 2}$ state were found to be $A (151) = -<#comment/> 228.84 (2) M H z$ , $B (151) = 226.9 (5) M H z$ and $A (153) = -<#comment/> 101.87 (6) M H z$ , $B (153) = 575.4 (1.5) M H z$ , which all agree with previously published results except for A(153), which shows a small discrepancy. The isotope shift is found to be 3163.8(6) MHz, which also has a discrepancy with previously published results.

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