Reactivity of UI4(OEt2)2 with phenols: probing the chemistry of the U-I bond.
Solutions of UI4(OEt2)2 in Et2O were found to deposit orange crystals of [H(OEt2)2][UI5(OEt2)] (1) upon standing at room temperature. The proton in the cation of 1 most likely originates from the surface of the glass vial in which the solution was stored. Reactions of UI4(OEt2)2 with 1 equiv. of ArOH in toluene, followed by addition of THF, provides UI3(OAr)(THF)x (Ar = Ph, x = 3, 2; Ar = 2,6-Ph2C6H3, x = 2, 3). UI4(OEt2)2 also reacts with 2 equiv. of ArOH (Ar = Ph, 4-tBuC6H4, 2,6-Me2C6H3, C6F5) in toluene, followed by addition of THF, to generate UI2(OC6H5)2(THF)3 (4), UI2(O-4-tBuC6H4)2(THF)3 (5), UI2(O-2,6-Me2C6H3)2(THF)3 (6) and UI2(OC6F5)2(THF)3 (7), in moderate yields. Complete conversion to the products requires the use of a dynamic vacuum to remove the HI generated upon addition of the phenol.
Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106, USA.
David D
DD
Schnaars
Guang
G
Wu
Trevor W
TW
Hayton