Separation of Isomers and Mechanisms of Inversion of Stereochemistry of Group 9 d<sup>6</sup> Tris-Chelate Complexes of Hinokitiol
Bibliographic record
Abstract
Tris-chelate complexes of Co(III), Rh(III), and Ir(III) with 4-isopropyltropolone (hinokitiol or β-thujaplicin) form by the substitution of carbonate and chloride ligands from group 9 trivalent metal salts. The new complexes are neutral, are readily soluble in most organic solvents, and are brightly colored with strong charge transfer bands. The fac isomers of Co(hino) 3 and Rh(hino) 3 were isolated from the mixture by fractional recrystallization from ethanol. The remaining mixtures were respectively enriched by 5:3 and 4.4:3 for the mer isomer. The 1 H NMR data show that the complexes exhibit remarkable stereochemical lability, which is unusual for diamagnetic d 6 group 9 metals, with rotational barriers of 14.2 and 18.2 kcal/mol found for the inversion of stereochemistry of Co(hino) 3 and Rh(hino) 3 . The low activation barriers, as well as the analysis of some key structural parameters, suggest that the inversion of stereochemistry occurs via a trigonal-twist (Bailar) mechanism. Facile substitution of a single hinokitiol ligand in the cobalt complex with ethylenediamine to form [Co(en)(hino) 2 ]Cl also indicates that the tris-chelates are substitutionally and configurationally labile.
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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) | 0.001 | 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".