“Crowned” Univalent Indium Complexes as Donors? Experimental and Computational Insights on the Valence Isomers of EE′X<sub>4</sub> Species
Bibliographic record
Abstract
The use of the univalent indium reagent [In([18]crown-6)][OTf] as a donor is investigated by its reactions with acceptors including InX(3) (X=Cl, Br, I). The donor-acceptor complexes of the form [X([18]crown-6)In-InX(3)] obtained in this manner represent the first new isomeric form of indium(II) halides identified for at least five decades. The formation of such complexes appears to be particularly favorable and they are isolated as products in many reactions involving low-valent indium, a halide source, and [18]crown-6. A convenient solution-phase synthesis of In[ECl(4)] salts is reported. This facile and direct syntheses of In[ECl(4)] (E=Al, Ga, In) salts allows for the in situ preparation and isolation of crown-ether complexes of the form [In([18]crown-6)][ECl(4)], whose existence had been postulated but never confirmed. Solution-phase and solid-state NMR experiments reveal that these compounds can exist as either donor-acceptor complexes or ionic salts, depending on the phase of the system, the nature of the solvent employed, and the identity of the metalate anion involved. Similar investigations into the effect of a smaller crown ether allow for the isolations of salts containing the cation [In([15]crown-5)](+). Computational investigations into the nature of the crowned univalent indium donor fragments, and on the donor-acceptor complexes produced, demonstrate the influence of anionic substituents on the reactivity of lone pair of electrons of the In(I) center. Natural bond orbital (NBO) analysis of donor-acceptor models shows that the composition of the E-E bond MO should provide the ability to predict which models should form stable complexes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
How this classification was reachedexpand
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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.004 | 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 teacher head, 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".