Put a Ring on It: Improving the Thermal Stability of Molybdenum Imides through Ligand Rigidification
Bibliographic record
Abstract
Volatile bis( tert -butylimido)-dichloromolybdenum(VI) compounds containing N,N’ -chelating ligands, ( t BuN) 2 MoCl 2 ·L, have previously been used as single-source precursors for the chemical vapor deposition of high-purity Mo 2 N thin films. The first step in the thermolysis of these compounds is the partial dissociation of the chelating ligand to yield ( t BuN) 2 MoCl 2, which further decomposes by eliminating isobutylene and t BuNH 2 . The rate-determining step in this process is the formation of a pentacoordinate intermediate where the previously bidentate ligand adopts a κ 1 -coordination. Here we show that rigidification of the ligand backbone, by incorporating various heterocycles, led to an overall increase in thermal stability (21–38 °C) of these complexes by preventing the formation of the κ 1 -intermediate. Formation of the κ 1 -intermediates is highlighted by high level calculations and is supported by experimental activation barriers. Finally, a model for the κ 1 -bipyridine adduct was isolated and characterized using 2-phenylpyridine. This careful control of the thermal stabilities of these compounds can lead to new vapor-phase deposition precursors for the preparation of Mo 2 N films.
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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) | 0.000 | 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) | 0.000 | 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".