Rhenium chemistry – Then and Now

Dilworth, Jonathan R.

doi:10.1016/j.ccr.2021.213822

Cited by 41 publications

(26 citation statements)

References 340 publications

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“…Complexes based on a Re(I) tricarbonyl core with a dinitrogenated ligand (N,N such as 1,10-phenanthroline or 2,2 0 -bipyridine derivatives) in the equatorial position, and halogen or pyridine derivatives as ancillary ligands (X), have been extensively used for diverse applications, including solar cells, 1,2 catalysis, [3][4][5][6][7][8] and more recently, biological applications, [9][10][11][12][13][14][15][16][17] including staining of bacteria, yeasts (walled cells), and proteins separated by SDS-PAGE. 18,19 Photophysical attributes of fac-[Re(I)(CO) 3 (N,N)X] n complexes (where n is 0 or 1+) can be modulated by combining the (N,N) and X ligands.…”

Section: Introductionmentioning

confidence: 99%

The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view

et al. 2021

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Section: Introductionmentioning

confidence: 99%

The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view

et al. 2021

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“…Indeed, our efforts with new ancillary ligands led to a host of interesting group 5 chemistry, − but of more relevance to this Account was our decision to target rhenium-BDI systems. We hypothesized that the marginal increase in electronegativity from niobium to rhenium and rhenium’s ability to access a wide range of oxidation states might increase our chances of isolating reactive low-valent species (specifically because Re is less likely than Nb to cleave the BDI ligand to form a higher-valent product). Additionally, by increasing the d-electron count by an even pair of electrons from Nb to Re, we left open the potential to access two-electron transformations similar to those in the Nb system using the same set of ligands .…”

Section: Synthesis Of a Re(i) Metalatementioning

confidence: 77%

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

et al. 2022

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Conspectus 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) β-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 Zn2 2+ 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 unconve...

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“…3,[7][8][9][10][11][12][13] Most recently, in 2021, Dilworth comprehensively surveyed and documented progress in rhenium coordination chemistry. 14 Commercially available rhenium sources have featured extensively as catalysts/precatalysts in chemical synthesis. Some examples are shown in Table 1, in addition to their important fundamental characteristics.…”

Section: Introductionmentioning

confidence: 99%