Reactivity of the cationic uranium amide compound [U(eta-C8H8)(NEt(2))(OC4H8)(2)][BPh(4)]

The cationic uranium amide compound [U(COT)(NEt(2))(THF)(2)][BPh(4)] 1 (COT=eta-C8H8, THF=tetrahydrofuran) reacted with the nucleophiles MX (LiCH(SiMe(3))(2), NaN(SiMe(3))(2), KC5H5, KC(5)Me(5), LiCl and KBH4) to give the corresponding neutral addition complexes [U(COT)(NEt(2))(X)]. Insertion of CO2, CS2 or MeCN into the U-N bond of 1 afforded respectively [U(COT)(E(2)CNEt(2))(THF)(2)][BPh(4)] (E=O or S) and [U(COT)(NC{Me}{NEt(2)})(THF)(2)][BPh(4)]. Reactions of 1 with the proton acidic molecules NEt(3)HCl, C5H6 and (i)PrEH (E=O or S) led to the formation of [U(COT)(Cl)(THF)(3)][BPh(4)], [U(COT)(C5H5)(THF)(2)][BPh(4)] and [U(COT)(E(i)Pr)(2)] respectively. The crystal structures of [U(COT)(NEt(2))(THF)(3)] [BPh(4)] and [U(COT)(S(2)CNEt(2))(THF)(2)][BPh(4)] have been determined.