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The reactivity of the cerium(IV) oxo complex [(L OE ) 2 Ce IV (═O)(H 2 O)]·MeC(O)NH 2 (1; L OE  - = [CoCp{P(O)(OEt) 2 } 3 ] - , where Cp = η 5 -C 5 H 5 ) toward electrophiles and Brønsted acids has been investigated. The treatment of 1 with acetic anhydride afforded the diacetate complex [Ce IV (L OE ) 2 (O 2 CMe) 2 ] (2). The reaction of 1 with B(C 6 F 5 ) 3 yielded [Ce IV (L OE ) 2 (Me 2 CONH 2 ) 2 ][B(C 6 F 5 ) 3 (OH)] 2 (3), in which the [B(C 6 F 5 ) 3 (OH)] - anions are H-bonded to the O-bound acetamide ligands. The treatment of 1 with HCl and HNO 3 afforded [Ce IV (L OE ) 2 Cl 2 ] and [Ce IV (L OE ) 2 (NO 3 ) 2 ], respectively. Protonation of 1 with triflic acid (HOTf) gave the diaqua complex [Ce IV (L OE ) 2 (H 2 O) 2 ](OTf) 2 (4), in which the triflate anions are H-bonded to the two aqua ligands. The treatment of 1 with phenol afforded the phenoxide complex [Ce IV (L OE ) 2 (OPh) 2 ] (5). The oxo-bridged bimetallic complex [(L OE ) 2 (Me 2 CONH 2 )Ce IV (O)NaL OE ] (6) with the Ce-O oxo and Na-O oxo distances of 1.953(4) and 2.341(4) Å, respectively, was obtained from the reaction of 1 with [NaL OE ]. Density functional theory calculations showed that the model complex [(L OMe ) 2 Ce IV (Me 2 CONH 2 )(O)NaL OMe ] (6A; L OMe  - = [CoCp{P(O)(OMe) 2 } 3 ] - ) contains a polarized Ce═O multiple bond. The energy for dissociation of the {NaL OMe } fragment from 6A in acetonitrile was calculated to be +33.7 kcal/mol, which is higher than that for dissociation of the H-bonded acetamide from [(L OMe ) 2 Ce IV (═O)(H 2 O)]·MeC(O)NH 2 (1A) (calculated to be +17.4 kcal/mol). In hexanes containing trace water, complex 1 decomposed readily to a mixture of a tetranuclear cerium(IV) oxo cluster, [Ce IV  4 (L OE ) 4 (μ 4 -O)(μ 2 -O) 4 (μ 2 -OH) 2 ] (7), and a cerium(III) complex, [Ce III (L OE ) 2 (H 2 O) 2 ][L OE ] [8(L OE )], whereas the cerium/sodium oxo complex 6 is stable under the same conditions. The crystal structures of 3, 4·H 2 O, 6, and 8(L OE ) have been determined.

Probing the Reactivity of the Ce═O Multiple Bond in a Cerium(IV) Oxo Complex