Hydroalumination of a Dinuclear Tantalum Dinitrogen Complex: N−N Bond Cleavage and Ancillary Ligand Rearrangement
Bibliographic record
Abstract
The addition of diisobutylaluminum hydride (DIBAL) to the side-on end-on dinitrogen complex ([NPN]Ta) 2 (μ-η 1:η 2 -N 2 )(μ-H) 2, 1 (where [NPN] = (PhNSiMe 2 CH 2 ) 2 PPh), is described. The two end products are diastereomeric rotational isomers in which N−N bond cleavage has occurred with an Al( i Bu)H group attached to one of the nitride atoms. The reaction proceeds through addition of DIBAL to 1 to generate a thermally sensitive intermediate that has been characterized in solution as the result of Al−H addition across the TaN 2 moiety, namely, ([NPN]TaH)(μ-η 1:η 2 -NNAl i Bu 2 )(μ-H) 2 (Ta[NPN), 2 . This material subsequently rearranges via a second thermally labile intermediate to ultimately generate two diastereomeric end products that show N−N bond cleavage, loss of H 2, loss of an aluminum isobutyl group, and NPN ligand migration from tantalum to aluminum. Both of these complexes have been isolated in crystalline form and analyzed by single-crystal X-ray diffraction. The second thermally sensitive intermediate has been characterized on the basis of multinuclear NMR spectroscopy as ([NPN]TaH)(μ-η 1:η 2 -NNAl i Bu(μ-H))(μ-H) 2 (Ta[NPN), 3 .
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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 | 0.001 | 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".