High-Valent Ni and Cu Complexes of a Tetraanionic Bis(amidateanilido) Ligand
Bibliographic record
Abstract
High-valent metal species are often invoked as intermediates during enzymatic and synthetic catalytic cycles. Anionic donors are often required to stabilize such high-valent states by forming strong bonds with the Lewis acidic metal centers while decreasing their oxidation potentials. In this report, we discuss the synthesis of two high-valent metal complexes [ML] + in which the Ni III and Cu III centers are ligated by a new tetradentate, tetraanionic bis(amidateanilido) ligand. [ML] +, obtained via chemical oxidation of ML, exhibits UV–vis–NIR, EPR, and XANES spectra characteristic of square planar, high-valent M III species, suggesting the locus of oxidation for both [ML] + is predominantly metal-based. This is supported by theoretical analyses, which also support the observed visible transitions as ligand-to-metal charge transfer transitions characteristic of square planar, high-valent M III species. Notably, [ML] + can also be obtained via O 2 oxidation of ML due to its remarkably negative oxidation potentials ( CuL / [CuL] +: −1.16 V, NiL / [NiL] +: −1.01 V vs Fc/Fc + in MeCN). This demonstrates the exceptionally strong donating nature of the tetraanionic bis(amidateanilido) ligation and its ability to stabilize high-valent metal centers..
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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 | 0.000 | 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) | 0.001 | 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".