7-Metalla-1,4-diphosphanorbornadienes: cycloaddition of monovalent group 13 NacNac complexes to a stable 1,4-diphosphinine
Bibliographic record
Abstract
This work presents the first example of a dienophilic property of the monovalent group-13 NacNac complexes, which are well-known for their carbene-like reactivity, e.g., addition to multiple bonds, insertion into single bonds, and oxidative cleavage of some multiple bonds. In reactions with imidazole-2-thione based tricyclic 1,4-diphospinine 4, the monovalent compounds NacNacM (M = Al,Ga) showed dienophilic behaviour and produced the corresponding 7-metalla-1,4-diphosphanorbornadienes (5-6), leaving the C[double bond, length as m-dash]S functionality of the imidazole-2-thione intact, while the NacNacIn complex did not show any reactivity because of unfavourable thermodynamics. DFT calculations revealed that for NacNacAl, the cycloaddition was kinetically more favoured (due to a small reaction barrier) than the oxidative cleavage of the C[double bond, length as m-dash]S functionality, despite the fact that the product of the C[double bond, length as m-dash]S bond addition has a somewhat higher stability. For NacNacGa, the cycloaddition reaction was both kinetically and thermodynamically favourable than the cleavage of C[double bond, length as m-dash]S. Furthermore, these reactions were found to be reversible in nature and diphosphinine 4 showed a clear preference towards Al than towards Ga which reflects the better inclination of Ga to stay monovalent than be in the trivalent state.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.056 | 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".