A Study of Silver (I) Ion−Organonitrile Complexes: Ion Structures, Binding Energies, and Substituent Effects
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Bibliographic record
Abstract
Density functional calculations at B3LYP/DZVP are used to obtain the binding enthalpies and free energies for the reaction Ag + + XCN → AgNCX +, where X = H, CH 3, NH 2, OH, F, CF 3, CN, NO 2, N(CH 3 ) 2, C 6 H 5, p -C 6 H 4 N(CH 3 ) 2, p -C 6 H 4 NO 2, and p -C 6 H 4 NH 2 . The calculated binding enthalpies at 298 K range from 52.2 kcal mol -1 for X = p -C 6 H 4 N(CH 3 ) 2 to 21.3 kcal mol -1 for X = NO 2 . Calculations at this level of theory are also used to optimize the structures of Ag(NCCH 3 ) n + and Ag(NCH) n + ions, where n = 1−6. The binding enthalpies for the addition of the first and second molecules of CH 3 CN are 40.1 and 35.3 kcal mol -1, whereas for HCN, they are calculated to be 31.2 and 28.3 kcal mol -1, respectively. The binding enthalpies of the third and fourth ligands are much smaller at 15.9 and 10.8 kcal mol -1 for CH 3 CN and 13.5 and 9.7 kcal mol -1 for HCN. The 5- and 6-coordinate structures have positive free energies of formation with both ligands. Electrospraying a solution of AgNO 3 and acetonitrile in water shows the dominant ions to be Ag +, AgNCCH 3 +, and Ag(NCCH 3 ) 2 +, with the Ag(NCCH 3 ) 3 + ion being observed only in very small amounts and only under relatively mild conditions. Energy-resolved collision-induced dissociation (CID) experiments confirm the Ag(NCCH 3 ) 3 + ion to be a loosely bound species, while the Ag(NCCH 3 ) 2 + and AgNCCH 3 + ions have substantially higher and comparable binding energies. Using the threshold method, we determined the binding energies at 0 K of NCCH 3 to Ag + and of NCCH 3 to AgNCCH 3 + to be 38.7 and 34.6 kcal mol -1, respectively; the corresponding energies at 298 K are 39.4 and 34.7 kcal mol -1 .
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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 it