Synthesis and transformations of 60-, 62-, and 64-electron Co<sub>4</sub>(CO)<i><sub>x</sub></i>(PNR<sub>2</sub>)<sub>2</sub> (<i>x</i> = 8, 9, 10) clusters
Bibliographic record
Abstract
A unique family of bis-(amino)phosphinidene Co4 clusters with electron counts in the 6064 e regime is described. The 62-electron (5 CoCo) butterfly compound [Co4(CO)8(µ-CO){µ3-P(TMP)}2] (TMP = 2,2,6,6-tetramethyl piperidyl) (1a) is obtained via condensation of the bridged (amino)phosphinidene complex [Co2(CO)6{µ-P(TMP)}]. Further heating and removal of CO gives the 60-electron (6 CoCo) tetrahedral compound [Co4(CO)6(µ-CO)2{µ3-P(TMP)}2] (3a). The reaction of K[Co(CO)4] with PCl2(N-i-Pr2) gives the 64-electron (4 CoCo) square-planar derivative [Co4(CO)8(µ-CO)2(µ4-PN-i-Pr2)2] (2), which loses one carbonyl ligand to form the 62-electron (5 CoCo) butterfly compound [Co4(CO)8(µ-CO)(µ3-PN-i-Pr2)2] (1b). Complex 1b releases another carbonyl to form the 60-electron (6 CoCo) tetrahedral compound [Co4(CO)6(µ-CO)2(µ3-PN-i-Pr2)2] (3b). X-ray structural analyses of compounds 1a, 1b, 2, and 3a have been carried out. The reversibility of the CO elimination reactions and the structural rearrangements accompanying changes in electron count in this series are discussed.Key words: cobalt, cluster compounds, phosphinidene, skeletal rearrangement.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 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) | 0.002 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".