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 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".