Applications of Low-Valent Transition Metalates: Development of a Reactive Noncarbonyl Rhenium(I) Anion.

Low-valent transition metalates─anionic, electronic-rich organometallic complexes─comprise a class of highly reactive chemical reagents that find integral applications in organic synthesis, small-molecule activation, transient species stabilization, and M-E bond formation, among others. The inherent reactivity of such electron-rich metal centers has necessitated the widespread use of strong backbonding ligands, particularly carbonyls, to aid in the isolation and handling of metalate reagents, albeit sometimes at the expense of partially masking their full reactivity. However, recent synthetic explorations into transition-metalate complexes devoid of archetypic back-bonding ligands have led to the discovery of highly reactive metalates capable of performing a variety of novel chemical transformations.Building on our group's long-standing interest in reactive organometallic species, a series of rational progressions in early-to-middle transition-metal chemistry ultimately led to our isolation of a rhenium(I) ß-diketiminate cyclopentadienide metalate that displays exceptional reactivity. We have found this Re(I) metalate to be capable of small-molecule activation; notably, the complex reversibly binds dinitrogen in solution and can be utilized to trap N2 for the synthesis of functionalized diazenido species. By employing isolobal analogues to N2 (CO and RNC), we were able to thoroughly monitor the mechanism of activation and conclude that the metalate's sodium counterion plays an integral role in promoting dinitrogen activation through a novel side-on interaction. The Re(I) metalate is also used in forming a variety of M-E bonds, including a series of uncommon rhenium-tetrylene (Si, Ge, and Sn) complexes that display varying degrees of multiple bonding. These metal tetrylenes act to highlight deviations in chemical properties within the group 14 elements. Our metalate's utility also applies to metal-metal bond formation, as demonstrated through the synthesis of a heterotetrametallic rhenium-zinc dimer. In this reaction, the Re(I) metalate performs a dual role as a reductant and metalloligand to stabilize a transient Zn22+ core fragment. Finally, the metalate displays unique reactivity with uranium(III) to yield the first transition metal-actinide inverse-sandwich bonds, in this case with three rhenium fragments bound through their Cp moieties surrounding the uranium center. Notably, throughout these endeavors we demonstrate that the metalate displays reactivity at multiple locations, including directly at the rhenium metal center, at a Cp carbon, through a Cp-sandwich mode, or through reversibly bound dinitrogen.Overall, the rhenium(I) metalate described herein demonstrates utility in diverse applications: small-molecule activation, the stabilization of reduced and/or unstable species, and the formation of unconventional M-E/M-M bonds or heterometallic complexes. Moving forward, we suggest that the continued discovery of noncarbonyl, electron-rich transition-metal anions featuring new or unconventional ligands should produce additional reactive organometallic species capable of stabilizing unique structural motifs and performing novel and unusual chemical transformations.

Heterobimetallic-Mediated Dinitrogen Functionalization: N-C Bond Formation at Rhenium-Group 9 Diazenido Complexes.

We report the synthesis and characterization of rhenium-group 9 heterobimetallic diazenido species (η5-Cp)Re(µ-BDI)(µ-N2)M(η4-COD) (1-M, M = Ir or Rh, Cp = cyclopentadienide, BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-ß-diketiminate, COD = 1,5-cyclooctadiene), formed from salt elimination reactions between Na[(η5-Cp)Re(BDI)] and [MCl(η4-COD)]2. Additionally, we find that these same reagents react under an argon atmosphere to instead produce bridging hydride complexes (BDI)Re(µ-η5:η1-C5H4)(µ-H)M(η4-COD) (2-M), which undergo rearrangements upon protonation to form the alternative bridging hydrides [(η5-Cp)Re(µ-BDI)(µ-H)M(η4-COD)][(B(m-C6H3(CF3)2)4)] (3-M). Further, we demonstrate the first example of N-C bond formation at a heterobimetallic dinitrogen complex through reactions of 1-M and methyl triflate, which produces the alkylated species [(η5-Cp)Re(µ-N(Me)N)(µ-BDI)M(η4-COD)][OTf] (4-M, OTf = trifluoromethanesulfonate). A combination of spectroscopic studies, X-ray structural analysis, and computational investigations is discussed as an aid to understanding the modes of dinitrogen activation within these unique heterobimetallic complexes.