Structural and Functional Characteristics of Rhenium Clusters Derived from Redox Chemistry of the Triangular [ReIII 3(μ-Cl)3] Core Unit

The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3 8+ core. Dissolution of 1 in HCl (6 M) generates [Re3(μ-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6−12 M) produces [(C6H5)4P]2[Re3(μ-Cl)3Cl7(H2O)2]·H2O (3), the structure of which features a planar [Re3(μ-Cl)3Cl3] framework (Re3 8+ core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII 2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3 8+-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[{Re3(μ-Cl)3Cl7(μ-OH)}2]·2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3 9+ triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[{Re3(μ-Cl)3Cl7(μ-Cl)}2]·10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1−3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(μ-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(μ-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(μ-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3 8+ cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(μ-Cl)3Cl7(CH3C(O)NH)]·CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(μ-Cl)3Cl8(MeOH)]·MeOH (10).