Bite Angle Effects of κ<sup>2</sup><i>P</i>-dppm vs κ<sup>2</sup><i>P</i>-dppe in Seven-Coordinate Complexes: A DFT Case Study
Bibliographic record
Abstract
This paper predicts the effects of replacing dppm (bis(diphenylphosphino)methane) with dppe (1,2-bis(diphenylphosphino)ethane) in seven-coordinate organometallic complexes by employing density functional theory (DFT) computations for a case example: WI 2 (CO)(κ 2 P-dppm)(η 2:η 2 -nbd) (nbd = norbornadiene), an intermediate in the W(II)-catalyzed ring-opening metathesis polymerization (ROMP) of nbd. Effects on both structure and ligand binding energy (i.e., reactivity) were investigated. For the known W–dppm complex (crystal structure provided here), of 37 energy-distinct stereoisomers found, only one low-energy stereoisomer is predicted, and it agrees with the known X-ray crystal structure, lending faith to the conformer search procedure. For the as yet unknown W–dppe complex, of 31 energy-distinct stereoisomers found, two low-energy stereoisomers are predicted. The computed DFT ligand binding energies {W–P, W–ene, W–CO, W + –I – } are {9, 17, 44, 102} kcal mol –1 for the W–dppm complex and {3, 15, 37, 95} for the W–dppe complex. The conclusion is that the increased PWP bite angle of dppe vs dppm will reduce all ligand binding energies due to increased interligand steric repulsion.
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.008 | 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".