Reaction of the Diimine Pyridine Ligand with Aluminum Alkyls: An Unexpectedly Complex Reaction
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Bibliographic record
Abstract
The diimine pyridine ligand 2,6-{2,6- i Pr 2 C 6 H 3 N CMe} 2 C 5 H 3 N ( 1 ) was reacted with a series of aluminum alkyls (Me 3 Al, Et 3 Al, i Bu 3 Al, i Bu 2 AlH, Et 2 AlCl). Depending on the choice of alkyl, addition to the imine carbon and the pyridine C2 and C4 positions was observed. Addition to C2 usually dominates but is reversible; the C4 alkylation product eventually dimerizes via double C−C coupling. Reaction of 1 with AlCl 3 gave the ionic complex [ 1 ·AlCl 2 ] + [AlCl 4 ] - . DFT calculations were used to support NMR assignments of the various addition products and also to study alkyl transfer from Et 2 AlCl to simplified model ligand 1 ‘. Direct alkyl transfer from coordinated Et 2 AlCl to the ligand C4 position is not possible. Introduction of a second molecule of Et 2 AlCl results in formation of the ion pair [ 1 ‘·AlEtCl] + [Et 3 AlCl] -, from which alkyl transfer to any position of the ligand is relatively easy. The dimerization of the C4-alkylated product is symmetry-forbidden and was calculated to follow a stepwise biradical path with an unusually low barrier.
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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 | 0.001 |
| 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) | 0.003 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
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