C(sp <sup>2</sup> )─H Bond Activation with a Heterometallic Nickel–Aluminium Complex
Bibliographic record
Abstract
Abstract Herein we present a ligand‐catalyzed bond‐breaking and making process that occurs with a Ni–Al heterometallic complex. While combinations of Ni pre‐catalysts and Al additives are known for site‐selective C─H functionalization, detailed studies of such systems are rare. Combining [Ni(COD) 2 ] and [(BDI)AlH 2 ] ( 1 ; BDI = 2,6‐diisopropylphenyl‐β‐methyldiketiminate) results in facile formation of a Ni–Al heterometallic complex [( η 4 ‐COD)Ni{( μ ‐H) 2 Al(BDI)}] ( 2 ; COD = 1,5‐cyclooctadiene). Once generated, this species can effect the C(sp 2 )─H activation of 4‐dimethylaminopyridine (DMAP) or pyridine with concomitant H 2 evolution, a process that is accelerated through addition of PCy 3 . The mechanism was studied through kinetics, kinetic isotope effects (KIEs), isotope labeling studies, and modeling. The reaction is 1 st order in PCy 3 and proceeds with a KIE of 0.9–1.1. Support is provided for a pathway involving the synergistic action of both metals, promoted by reversible coordination of the phosphine. The data suggest that both C─H oxidative addition and H 2 reductive elimination steps in this system are readily accessible and are not rate limiting. This finding has implications for future catalyst design using combinations of Ni and Al metals and suggests that control of ligand exchange steps may be the most important consideration in determining the rate of reaction.
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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 | 0.001 |
| 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)
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".