Reductive silylation of Cp*UO2((Mes)PDI(Me)) promoted by Lewis bases

Dalton Transactions : an International Journal of Inorganic Chemistry
John J KiernickiSuzanne C Bart

Abstract

Functionalization of the uranyl moiety (UO2(2+)) in Cp*UO2((Mes)PDI(Me)) (1-PDI) ((Mes)PDI(Me) = 2,6-((Mes)N[double bond, length as m-dash]CMe)2C5H3N; Mes = 2,4,6-triphenylmethyl), which bears a reduced, monoanionic pyridine(diimine) ligand, is reported. Silylating reagents, R3Si-X (R = Me, X = Cl, I, OTf, SPh; R = Ph, X = Cl), effectively add across the strong O[double bond, length as m-dash]U[double bond, length as m-dash]O bonds in the presence of the Lewis base, OPPh3, generating products of the form (R3SiO)2UX2(OPPh3)2 (R = Me, X = I (2-OPPh3), Cl (3-OPPh3), SPh (5-OPPh3), OTf (6-OPPh3); R = Ph, X = Cl (4-OPPh3)). During this transformation, reduction to uranium(iv) occurs with loss of (Cp*)2 and (Mes)PDI(Me), each of which acts as a one-electron source. In the reaction, the Lewis base serves to activate the silyl halide, generating a more electrophilic silyl group, as determined by (29)Si NMR spectroscopy, that undergoes facile transfer to the oxo groups. Complete U-O bond scission was accomplished by treating the uranium(iv) disiloxide compounds with additional silylating reagent, forming the family (Ph3PO)2UX4. All compounds were characterized by (1)H NMR, infrared, and electronic absorption spectroscopies. X-ray crysta...Continue Reading

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Citations

Dec 19, 2016·Angewandte Chemie·John J KiernickiSuzanne C Bart
Mar 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Polly L ArnoldRowan D Young
Nov 20, 2016·Chemistry : a European Journal·Giuseppe Trusso SfrazzettoAntonino Gulino
Apr 21, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michela L MaiolaEllen M Matson
May 14, 2021·Inorganic Chemistry·Taylor V FetrowScott R Daly
Apr 16, 2020·Journal of the American Chemical Society·Mikiyas K AssefaTrevor W Hayton
Dec 12, 2018·Journal of the American Chemical Society·Ezra J CoughlinSuzanne C Bart
Jun 4, 2020·Inorganic Chemistry·Greggory T KentTrevor W Hayton
Oct 24, 2020·Inorganic Chemistry·Robert J WardJustin R Walensky

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