Reactivity of the cationic uranium amide compound [U($\eta$-$C_{5}$$Me_{5}$$)_{2}$(N$Me_{2}$)(O$C_{4}$$H_{8}$)][B$Ph_{4}$]
Résumé
The cationic uranium amide compound [U($Cp^{∗}$$)_{2}$(N$Me_{2}$)(THF)][B$Ph_{4}$] 1 (($Cp^{∗}$ = $\eta$-$C_{5}$$Me_{5}$, THF = tetrahydrofuran) was transformed into the heterocyclic metallacycle |(($Cp^{∗}$$)_{2}$U(O(C$H_{2}$$)_{4}$N$Me_{2}$((C$H_{2}$$)_{4}$O)B$Ph_{4}$| ·0.5THF 2 in the presence of a catalytic amount of the free amine N$R_2$H (R = Me, Et). Treatment of 1 with $^{t}Bu$NC afforded the isocyanide adduct [U($Cp^{∗}$$)_{2}$(N$Me_{2}$)(CN$^{t}Bu$$)_{2}$][B$Ph_{4}$] whereas reactions with MeCN, C$O_2$ and CO gave the insertion compounds [U($Cp^{∗}$$)_{2}$(NC{Me}{N$Me_{2}$})(THF)][B$Ph_{4}$] 5, [U(($Cp^{∗}$$)_{2}$ ($O_{2}$CN$Me_{2}$)(THF)][B$Ph_{4}$] 6 and [U(($Cp^{∗}$$)_{2}$($\eta_{2}$-CON$Me_{2}$)(THF)][B$Ph_{4}$] 7. The crystal structure of a THF solvate of 4 has been determined.