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The oxo- and catecholate-bridged U IV /U IV Pacman complex [{(py)U IV OU IV (μ-O 2 C 6 H 4 )(py)}(L A )] A (L A = a macrocyclic "Pacman" ligand; anthracenylene hinge between N 4 -donor pockets, ethyl substituents on meso -carbon atom of each N 4 -donor pocket) featuring a bent U IV -O-U IV oxo bridge readily reacts with small molecule substrates to undergo either oxo-atom functionalisation or substitution. Complex A reacts with H 2 O or MeOH to afford [{(py)U IV (μ-OH) 2 U IV (μ-O 2 C 6 H 4 )(py)}(L A )] ( 1 ) and [{(py)U IV (μ-OH)(μ-OMe)U IV (μ-O 2 C 6 H 4 )(py)}(L A )] ( 2 ), respectively, in which the bridging oxo ligand in A is substituted for two bridging hydroxo ligands or one bridging hydroxo and one bridging methoxy ligand, respectively. Alternatively, A reacts with either 0.5 equiv. of S 8 or 4 equiv. of Se to provide [{(py)U IV (μ-η 2 :η 2 -E 2 )U IV (μ-O 2 C 6 H 4 )(py)}(L A )] (E = S ( 3 ), Se ( 4 )) respectively, in which the [E 2 ] 2- ion bridges the two U IV centres. To the best of our knowledge, complex A is the first example of either a d- or f-block bimetallic μ-oxo complex that activates elemental chalcogens. Complex A also reacts with XeF 2 or 2 equiv. of Me 3 SiCl to provide [{(py)U IV (μ-X) 2 U IV (μ-O 2 C 6 H 4 )(py)}(L A )] (X = F ( 5 ), Cl ( 6 )), in which the oxo ligand has been substituted for two bridging halido ligands. Reacting A with either XeF 2 or Me 3 SiCl in the presence of O(Bcat) 2 at room temperature forms [{(py)U IV (μ-X)(μ-OBcat)U IV (μ-O 2 C 6 H 4 )(py)}(L A )] (X = F ( 5A ), Cl ( 6A )), which upon heating to 80 °C is converted to 5 and 6 , respectively. In order to probe the importance of the bent U IV -O-U IV motif in A on the observed reactivity, the bis(boroxido)-U IV /U IV complex, [{(py)(pinBO)U IV OU IV (OBpin)(py)}(L A )] ( B ), featuring a linear U IV -O-U IV bond angle was treated with H 2 O and Me 3 SiCl. Complex B reacts with two equiv. of either H 2 O or Me 3 SiCl to provide [{(py)HOU IV OU IV OH(py)}(L A )] ( 7 ) and [{(py)ClU IV OU IV Cl(py)}(L A )] ( 8 ), respectively, in which reactions occur preferentially at the boroxido ligands, with the μ-oxo ligand unchanged. The formal U IV oxidation state is retained in all of the products 1-8 , and selective reactions at the bridging oxo ligand in A is facilitated by: (1) its highly nucleophilic character which is a result of a non-linear U IV -O-U IV bond angle causing an increase in U-O bond covalency and localisation of the lone pairs of electrons on the μ-oxo group, and (2) the presence of the bridging catecholate ligand, which destabilises a linear oxo-bridging geometry and stabilises the resulting products.

Selective oxo ligand functionalisation and substitution reactivity in an oxo/catecholate-bridged UIV/UIV Pacman complex

Selective oxo ligand functionalisation and substitution reactivity in an oxo/catecholate-bridged U^IV/U^IV Pacman complex