Phosphorus magnetic shielding tensors for transition-metal compounds containing phosphine, phosphido, and phosphinidene ligands: Insights from computational chemistry
Bibliographic record
Abstract
The present study examines the quality of the restricted HartreeFock (RHF) ab initio, B3LYP hybrid density functional theory (DFT), and relativistic zeroth-order regular approximation (ZORA) DFT methods for the calculation of phosphorus chemical shift (CS) tensors in phosphine, phosphido, and phosphinidene transition-metal complexes. A detailed comparison of calculated and experimental 31 P CS tensors allows us to identify the characteristic advantages of each computational method. The results from B3LYP and ZORA-DFT calculations indicate that a double-ζ quality basis set reproduces experimental values of the principal components of the 31 P CS tensor in many of the phosphorus-containing transition-metal complexes investigated, whereas the RHF method requires a triple-ζ doubly polarized basis set, yet fails in the case of the terminal phosphido group. Inclusion of the spin-orbit relativistic correction with the ZORA-DFT formalism requires a triple-ζ quality basis set to reproduce the experimental data. We demonstrate the merit of modern computational methods for investigating theoretically the effect of geometric variations upon the phosphorus CS tensor by systematically altering the WP bond length and the W-P-C Me bond angle in W(CO) 5 (PMe 3 ). Additionally, a previously reported correlation, determined experimentally, relating the 31 P CS tensor to the Fe-P-Fe bond angle in a series of iron phosphido-bridging compounds, has been reproduced with calculations using the model compound Fe 2 (CO) 6 (µ 2 -PPh 2 )(µ 2 -Cl). The results presented demonstrate the value of modern computational techniques for obtaining a greater understanding of the relationship between phosphorus chemical shifts and molecular structure.Key words: 31 P chemical shift, phosphine, phosphido, phosphinidene, RHF, B3LYP, relativistic, ZORA-DFT.
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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".