Electronic Effects in the Oxidative Addition of Iodomethane with Mixed-Aryl β-Diketiminate Chromium Complexes
Bibliographic record
Abstract
The Cr II complexes CpCr[DppNC(Me)CHC(Me)NC 6 H 4 Y] ( 1; Dpp = 2,6-(Me 2 CH) 2 C 6 H 3 ) were used to prepare the corresponding Cr III iodo ( 2 ) and methyl ( 3 ) mixed-aryl β-diketiminate compounds with Y = OMe ( a ), CH 3 ( b ), H ( c ), CF 3 ( d ). Oxidation of the Cr II precursors with iodine gave CpCr[DppNC(Me)CHC(Me)NC 6 H 4 Y](I) ( 2a − d ). The Cr III methyl compounds 3a − d were prepared by reaction of the Cr II complexes with iodomethane followed by MeMgI. The Cr III chloride complexes 4a − d were synthesized by salt metathesis of isolated CpCrCl 2 (THF) with the appropriate deprotonated mixed-aryl β-diketiminate. The structures of the paramagnetic complexes 1b, c, 2a, b, 3a − d, and 4a − d were determined by single-crystal X-ray diffraction. The rate constants for the single-electron oxidative addition of iodomethane with 1a − d were determined by monitoring the reaction by UV−vis spectroscopy. The rate constants correlated well with the electronic parameters of the Y substituents (ρ = −0.36). The rate constants for 1a − d were an order of magnitude greater than those previously obtained for the same reaction with CpCr[(DppNCMe) 2 CH] and related ortho-disubstituted symmetric β-diketiminate complexes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.019 | 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".