Acceleration of the methanolysis of phosphate diesters promoted by La(OTf)<sub>3</sub> The analysis of non-integer pH/rate profiles resulting from changes in metal ion speciation
Bibliographic record
Abstract
In a previous publication (A.A. Neverov and R.S. Brown. Inorg. Chem. 40, 3588 (2001)) we reported very effective catalysis of the methanolysis of some phosphate diesters (methyl p-nitrophenyl phosphate (1), bis(p-nitrophenyl) phosphate (2), and diphenyl phosphate (3)) promoted by La3+, and noted a general observation that the plots of logkcat vs. [Formula: see text]pH had non-integer gradients. In this report the origins of that behaviour are studied and analyzed through determination of the speciation of La3+(OCH3)n, (La3+)2(OCH3)m, (La3+)2:phosphate:(OCH3)y forms in solution as a function of [Formula: see text]pH. Potentiometric titrations of solutions of La(OTf)3 in methanol at low (<1 × 104 mol/L) and high (>1 × 103 mol/L) concentration were analyzed through fits of the data to various models to provide speciation diagrams of the various La3+ forms in the absence of phosphate. Titrations of La3+ in the presence of diphenyl phosphate were also analyzed to provide speciation diagrams for phosphate bound forms. The kinetic data for the La3+ catalyzed methanolysis of 1 were analyzed through fitting the kinetic data at low and high [La3+] as a function of [Formula: see text]pH to a linear combination of the individual kinetic contributions of each species. Overall the data are best analyzed in the low [La3+] domain as resulting from methoxide attack on a transient complex of phosphate bound to La3+(OCH3)0,1. In the high [La3+] domain the data fit two kinetically equivalent processes involving either a spontaneous decomposition of (La3+)2:1:(OCH3)2,3,4,5 or external methoxide attack on (La3+)2:1:(OCH3)1,2,3,4. Key words: lanthanides, phosphate diester, methanolysis, kinetics, speciation, metal ion catalysis of methanolysis, DNA model methanolysis.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".