An Investigation of 1:1 Adducts of Gallium Trihalides with Triarylphosphines by Solid‐State <sup>69/71</sup>Ga and <sup>31</sup>P NMR Spectroscopy
Bibliographic record
Abstract
Several 1:1 adducts of gallium trihalides with triarylphosphines, X(3)Ga(PR(3)) (X=Cl, Br, and I; PR(3)=triarylphosphine ligand), were investigated by using solid-state (69/71)Ga and (31)P NMR spectroscopy at different magnetic-field strengths. The (69/71)Ga nuclear quadrupolar coupling parameters, as well as the gallium and phosphorus magnetic shielding tensors, were determined. The magnitude of the (71)Ga quadrupolar coupling constants (C(Q)((71)Ga)) range from approximately 0.9 to 11.0 MHz. The spans of the gallium magnetic shielding tensors for these complexes, δ(11)-δ(33), range from approximately 30 to 380 ppm; those determined for phosphorus range from 10 to 40 ppm. For any given phosphine ligand, the gallium nuclei are most shielded for X=I and least shielded for X=Cl, a trend previously observed for In(III)-phosphine complexes. This experimental trend, attributed to spin-orbit effects of the halogen ligands, is reproduced by DFT calculations. The signs of C(Q)((69/71)Ga) for some of the adducts were determined from the analysis of the (31)P NMR spectra acquired with magic angle spinning (MAS). The (1)J((69/71)Ga,(31)P) and ΔJ((69/71)Ga, (31)P) values, as well as their signs, were also determined; values of (1)J((71)Ga,(31)P) range from approximately 380 to 1590 Hz. Values of (1)J((69/71)Ga,(31)P) and ΔJ((69/71)Ga,(31)P) calculated by using DFT have comparable magnitudes and generally reproduce experimental trends. Both the Fermi-contact and spin-dipolar Fermi-contact mechanisms make important contributions to the (1)J((69/71)Ga,(31)P) tensors. The (31)P NMR spectra of several adducts in solution, obtained as a function of temperature, are contrasted with those obtained in the solid state. Finally, to complement the analysis of NMR spectra for these adducts, single-crystal X-ray diffraction data for Br(3)Ga[P(p-Anis)(3)] and I(3)Ga[P(p-Anis)(3)] were obtained.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 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".