Computational Study of Tungsten(II)-Catalyzed Rearrangements of Norbornadiene
Bibliographic record
Abstract
Rearrangements of norbornadiene (NBD, C7H8) to various alkylidenes, via a hypothetical 7-coordinate tungsten(II) complex W(CO)3I2(NBD), were studied using density-functional theory computations. An extensive search for intermediates and transition states of rearrangement was made. The theoretical method (basis sets and level of DFT) used was justified by new benchmark studies which compare optimized structural parameters to those from crystal structures of several different tungsten complexes. Transition-metal-catalyzed rearrangements of NBD are not as well-known as those of norbornene and are considerably more complicated than had been thought. This work predicts a large variety of intermediates which may be feasible targets for experimental synthesis. All the rearrangement paths to alkylidenes found here feature high activation energies of over 45 kcal mol(-1), implying that self-initiation for the ring-opening metathesis polymerization of NBD via tungsten(II) complexes must occur via an alternative mechanism.
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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".