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Title: High-Resolution X-ray Photoelectron Spectroscopy of Organometallic (C 5 H 4 SiMe 3 ) 3 Ln III and [(C 5 H 4 SiMe 3 ) 3 Ln II ] 1– Complexes (Ln = Sm, Eu, Gd, Tb)
Authors:
; ; ; ; ; ;
Award ID(s):
2102568 1855328
Publication Date:
NSF-PAR ID:
10331831
Journal Name:
Journal of the American Chemical Society
Volume:
143
Issue:
40
Page Range or eLocation-ID:
16610 to 16620
ISSN:
0002-7863
Sponsoring Org:
National Science Foundation
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  1. The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′more »3 Ln compounds.« less