High-Resolution X-ray Photoelectron Spectroscopy of Organometallic (C5H4SiMe3)3LnIII and [(C5H4SiMe3)3LnII]1– Complexes (Ln = Sm, Eu, Gd, Tb)

Autor:	Daniel N. Huh, William J. Evans, Jared P. Bruce, John C. Hemminger, Sree Ganesh Balasubramani, Filipp Furche, Sierra R. Ciccone
Rok vydání:	2021
Předmět:	Lanthanide Valence (chemistry) Chemistry General Chemistry Electronic structure Biochemistry Catalysis Ion Metal Crystallography Colloid and Surface Chemistry X-ray photoelectron spectroscopy visual_art visual_art.visual_art_medium Density functional theory Electron configuration
Zdroj:	Journal of the American Chemical Society. 143:16610-16620
ISSN:	1520-5126 0002-7863
DOI:	10.1021/jacs.1c06980
Popis:	The capacity of X-ray photoelectron spectroscopy (XPS) to provide information on the electronic structure of molecular organometallic complexes of Ln(II) ions (Ln = lanthanide) has been examined for the first time. XPS spectra were obtained on the air-sensitive molecular trivalent 4fn Cp'3LnIII complexes (Ln = Sm, Eu, Gd, Tb; Cp' = C5H4SiMe3) and compared to those of the highly reactive divalent complexes, [K(crypt)][Cp'3LnII] (crypt = 2.2.2-cryptand), which have either 4fn+1 (Sm, Eu) or 4fn5d1 electron configurations (Gd, Tb). The Ln 4d, Si 2p, and C 1s regions of the Ln(III) and Ln(II) complexes were identified and compared. The metal 4d peaks of these molecular lanthanide complexes were used diagnostically to compare oxidation states. The valence region of the Gd(III) and Gd(II) complexes was also examined with XPS and density function theory/random phase approximation (DFT/RPA) calculations, and this led to the tentative assignment of a signal from the 5d1 electron consistent with a 4f75d1 electron configuration for Gd(II).
Databáze:	OpenAIRE
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