A comparative analysis of hydrosilative amide reduction catalyzed by first-row transition metal (Mn, Fe, Co, and Ni) <i>N</i>-phosphinoamidinate complexes
Bibliographic record
Abstract
A comparative study of the performance of (PN)M(N(SiMe3)2) (M = Mn, Fe, Co, and Ni) pre-catalysts supported by N-phosphinoamidinate ligation, as well as M(N(SiMe3)2)n (M = Li, Na, K, Mn, Fe, and Co) pre-catalysts, in the hydrosilative reduction of selected tertiary amide test substrates using PhSiH3 is reported. Encouraged by the performance observed herein for (PN)Ni(N(SiMe3)2) in the reduction of both N,N-dibenzylbenzamide and N,N-diisopropylbenzamide, further competitive testing involving the known complex (PN)Ni(NHdipp) (dipp = 2,6-diisopropylphenyl), as well as the new and crystallographically characterized mononuclear complexes (PN)Ni(OR) (R = 2,6-dimethylphenyl or tBu), revealed (PN)Ni(OtBu) to be particularly effective in such reduction chemistry, including transformations involving the secondary amides N-benzylbenzamide and caprolactam.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.000 | 0.001 |
| 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 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".