Structure of Uranium(V) Methyl and Uranium(IV) Ylide Complexes
2023; American Chemical Society; Volume: 42; Issue: 12 Linguagem: Inglês
10.1021/acs.organomet.3c00040
ISSN1520-6041
AutoresPokpong Rungthanaphatsophon, Kurtis Stanistreet-Welsh, Robert J. Ward, Steven P. Kelley, Wayne W. Lukens, Andrew Kerridge, Justin R. Walensky,
Tópico(s)Coordination Chemistry and Organometallics
ResumoSyntheses of rare examples of U(V) methyl and U(IV) ylide complexes are reported. Reaction of the previously reported U(IV) imido complex [(C5Me5)2U(py)(═NMes)] (py = pyridine, and Mes = 2,4,6-Me3C6H2) with CuI forms the U(V) complex [(C5Me5)2U(I)(═NMes)]. Reaction of the iodo complex with MgMe2 produces the methyl complex [(C5Me5)2U(CH3)(═NMes)]. The methyl complex was reacted with CH2PPh3, surprisingly forming [(C5Me5)2U(CH2PPh3)(═NMes)], a U(IV) ylide. This is formed from a disproportionation of a transient U(V) carbene, leading to the U(IV) ylide and a U(VI) bis(imido) complex, [(C5Me5)2U(═NMes)2]. These complexes were characterized using spectroscopic methods (nuclear magnetic resonance, infrared, and ultraviolet–visible–nean infrared), SQUID magnetometry, and X-ray crystallography, and density functional theory calculations are used to compare the U(V) methyl with the targeted U(V) carbene ligands.
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