A Fractional Bond Order of 1/2 in Pd25+−Formamidinate Species; The Value of Very High-Field EPR Spectra
| العنوان: | A Fractional Bond Order of 1/2 in Pd25+−Formamidinate Species; The Value of Very High-Field EPR Spectra |
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| المؤلفون: | Eckhard Bill, J. Micah North, Eberhard Bothe, Saritha Nellutla, Dino Villagrán, Carlos A. Murillo, John F. Berry, F. Albert Cotton, Narpinder Kaur, Chun Y. Liu, Naresh S. Dalal, Sergey A. Ibragimov |
| المصدر: | Journal of the American Chemical Society. 129:1393-1401 |
| بيانات النشر: | American Chemical Society (ACS), 2007. |
| سنة النشر: | 2007 |
| مصطلحات موضوعية: | Analytical chemistry, Crystallography, X-Ray, Electrochemistry, Biochemistry, Catalysis, Spectral line, law.invention, Paramagnetism, Colloid and Surface Chemistry, law, Organometallic Compounds, Anisotropy, Electron paramagnetic resonance, Spectroscopy, Line (formation), Formamides, Chemistry, Electron Spin Resonance Spectroscopy, Temperature, General Chemistry, Bond order, Spectrophotometry, Ultraviolet, Oxidation-Reduction, Palladium, Toluene |
| الوصف: | Reaction of Pd(2)(DAniF)(4), 1, (DAniF = di-p-anisylformamidinate) with 1 equiv of AgPF(6) in CH(2)Cl(2) at or below -10 degrees C produces the paramagnetic species [Pd(2)(DAniF)4]PF(6), 1-PF(6), that has been studied by X-ray crystallography, UV-vis spectroscopy, electrochemistry, and multifrequency (9.5, 34.5, 110, and 220 GHz) EPR spectroscopy. Upon oxidation of the precursor, the Pd-Pd distance decreases by 0.052 Angstrom from 2.6486(8) to 2.597(1) Angstrom. The EPR spectra show broad signals with line widths of about 1000 G. The spectra collected at high field show a large spread of g tensor components ( approximately 0.03), but these are masked at lower frequencies (9.5 and 34.5 GHz). A reinvestigation using high-field EPR of the p-tolyl analogue, which is the only other structurally characterized Pd(2)(5+) species (Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J. Am. Chem. Soc. 1988, 110, 1144), shows that this species, which had been reported to give an isotropic 9.5 GHz EPR spectrum, also gives anisotropic 110 and 220 GHz EPR spectra with a similarly large spread of g tensor components consistent with the unpaired electron residing in a metal-based MO. The results of these studies and calculations using density functional theory are consistent with the oxidation being metal-based, resulting in an uncommon Pd(2)(5+) species with a Pd-Pd bond order of 1/2. |
| تدمد: | 1520-5126 0002-7863 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::5bc012240c1142c1fa1b22386deebde9 https://doi.org/10.1021/ja067328y |
| رقم الأكسشن: | edsair.doi.dedup.....5bc012240c1142c1fa1b22386deebde9 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205126 00027863 |
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