Anionic Fullerene-60 Complexes of Manganese(−I), Cobalt(−I), and Rhenium(−I): Thermal and Photoinduced Electron Transfer Processes between Metal Carbonylate Anions and C<sub>60</sub>
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Bibliographic record
Abstract
Thermal and photochemical reactions of THF solutions of the carbonylate salts A[Mn(CO) 5 ], A[Co(CO) 4 ], and A[Re(CO) 5 ] (A = Na, PPN) with suspensions of C 60 result in electron transfer to give [C 60 ] - and the transient 17-electron, metal-centered radicals Mn(CO) 5, Co(CO) 4, and Re(CO) 5, respectively. However, the ensuing secondary processes vary significantly, depending on the metal and the reaction conditions. With manganese and rhenium, self-coupling of M(CO) 5 (M = Mn, Re) to give the metal−metal bonded dimers M 2 (CO) 10 and coupling of M(CO) 5 with [C 60 ] - to give the η 2 -C 60 complexes A[Mn(CO) 4 (η 2 -C 60 )] both occur under thermal and photochemical conditions. In contrast, the photochemical processes ultimately result also in complete homolysis of the dimers and regeneration of the metal-centered radicals, which then combine with fulleride ion [C 60 ] - still remaining in solution to form more of the η 2 -C 60 complexes. In the case of cobalt, no Co 2 (CO) 8 is formed, but the η 2 -C 60 complex [Co(CO) 3 (η 2 -C 60 )] - is produced. While the latter is thermally unstable in refluxing THF, undergoing decarbonylation to the previously reported mixed metal fulleride compound NaCoC 60 ·3THF, it is thermally stable under photochemical conditions at room temperature. Spectroscopic evidence suggests that much of the negative charge in [Mn(CO) 4 (η 2 -C 60 )] - is delocalized onto the fullerene ligand; as a result, the η 2 -C 60 −Mn bond is unusually strong and the complex [Mn(CO) 4 (η 2 -C 60 )] - is very stable, exhibiting little of the chemistry associated with either neutral η 2 -C 60 complexes or the analogous [Mn(CO) 5 ] - .
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it