Reactivity of low-valent iridium thiolate complexes
Bibliographic record
Abstract
A series of six-coordinate iridium thiol complexes, HIr(SR)(X)L2 where R = C6H5, C6H4CH3, or C6H4NO2, X = Cl or I and L = P(C6H5)3 or (C6H5)2PC2H4P(C6H5)2, have been synthesized by oxidative addition of four-coordinate precursors.Another series of metal complexes containing sulfur-rich ligands with the formula, M(SxCC6H4CH3) or M(SxCC6H5) where M = Zn, Ni or Co have been prepared as well.The infrared and nuclear magnetic resonance spectra of these complexes are discussed with regard to possible structures for the isomers these compounds tend to form under varying conditions.Some of these results help to confirm the large trans effect some of these ligands have within their respective complexes and are reconfirmed by the crystal structures obtained in these studies.The alpha effect of lone pair-bearing substituents was also explored with focus on the enhanced nucleophilicity of adjacent thiol groups.The results of these studies are further described in this thesis.RESUMÉ Une série de six-coordonnés composés de thiol iridium, HIr(SR)(X)L2 où R = C6H5, C6H4CH3, ou C6H4NO2, X = Cl ou I, et L = P(C6H5)3 ou (C6H5)2PC2H4P(C6H5)2, a été synthétisée par addition-oxydante, en commençant par les précurseurs de quatre-coordonnés.Une autre série de complexes métalliques contenant des ligands riches en soufre ayant la formule, M(SxCC6H4CH3) ou M(SxCC6H5), où M = Zn, Ni ou Co, a été préparé aussi.Les spectres d'infrarouge (IR) et les spectres de résonance magnétique nucléaire (RMN) ont été analysés pour la détermination des structures des isomères de ces composés qui se sont formé dans des conditions variables.Les résultats obtenus ont permis de confirmer l'effet trans au niveau de certains ligands de ces complexes.Ceci a également été confirmé par l'analyse des structures cristallines obtenus de ces composés.Les résultats de ces études sont décrits en detail dans le présent mémoire.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 source (direct Gemma or distilled Codex), 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".