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Involvement of a binuclear species with the Re-C(O)O-Re moiety in CO2 reduction catalyzed by tricarbonyl rhenium(I) complexes with diimine ligands: strikingly slow formation of the Re-Re and Re-C(O)O-Re species from Re(dmb)(CO)3S (dmb = 4,4'-dimethyl-2,2'-bipyridine, S = solvent).
| Content Provider | Semantic Scholar |
|---|---|
| Author | Hayashi, Yukiko Kita, Shouichi Brunschwig, Bruce S. Fujita, Etsuko |
| Copyright Year | 2003 |
| Abstract | Excited-state properties of fac-[Re(dmb)(CO)(3)(CH(3)CN)]PF(6), [Re(dmb)(CO)(3)](2) (where dmb = 4,4'-dimethyl-2,2'-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH(3)CN or THF. The one-electron reduced monomer, Re(dmb)(CO)(3)S (S = CH(3)CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)(CO)(3)(CH(3)CN)]PF(6) or by homolysis of [Re(dmb)(CO)(3)](2). In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)(3)S dimerizes slowly in THF, k(d) = 40 +/- 5 M(-1) s(-1). This rate constant is much smaller than those of other organometallic radicals which are typically 10(9) M(-1) s(-1). The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K approximately 10(-4)). The reaction of Re(dmb)(CO)(3)S with CO(2) is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO)(3)](2) in the presence of CO(2) produces CO with a 25-50% yield based on [Re]. A CO(2) bridged dimer, (CO)(3)(dmb)Re-CO(O)-Re(dmb)(CO)(3) is identified as an intermediate. Both [Re(dmb)(CO)(3)](2)(OCO(2)) and Re(dmb)(CO)(3)(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected. |
| File Format | PDF HTM / HTML |
| DOI | 10.1021/ja035960a |
| PubMed reference number | 14505419 |
| Journal | Medline |
| Volume Number | 125 |
| Issue Number | 39 |
| Alternate Webpage(s) | http://authors.library.caltech.edu/76680/2/ja035960asi20030710_025231.pdf |
| Alternate Webpage(s) | http://authors.library.caltech.edu/76680/3/ja035960asi20030710_025400.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/ja035960a |
| Journal | Journal of the American Chemical Society |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
