Artigo Acesso aberto Revisado por pares

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

ISSN

1520-6041

Autores

Pokpong Rungthanaphatsophon, Kurtis Stanistreet-Welsh, Robert J. Ward, Steven P. Kelley, Wayne W. Lukens, Andrew Kerridge, Justin R. Walensky,

Tópico(s)

Coordination Chemistry and Organometallics

Resumo

Syntheses 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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