Iron-SNS and -CNS Complexes: Selective C<sub>aryl</sub>–S Bond Cleavage and Amine-Borane Dehydrogenation Catalysis
Bibliographic record
Abstract
The synthesis, structure, and reactivity of an electron-rich FeII thioether-imine-thiolate complex, [Fe(SMeNS)(PMe3)3](OTf) (1-SNS), prepared by reaction of Fe(OTf)2(PMe3)4 with the SMeNHS ligand in THF, are reported (OTf = CF3SO3). Substitution reactions of 1 with mono- and bidentate donor ligands afforded [Fe(SMeNS)L(PMe3)2](OTf) (2,3-SNS; L = P(OMe)3, CNxylyl) and [Fe(SMeNS)(dmpe)(PMe3)](OTf) [4-SNS; dmpe = 1,2-bis(dimethylphosphino)ethane]. Heating 1-SNS in THF at 60 °C gave a new trivalent aryl-imine-thiolate complex, [Fe(CNS)(PMe3)3](OTf) (1-CNS) via Caryl–S bond cleavage. Reduction of 1-CNS with cobaltocene yielded divalent [Fe(CNS)(PMe3)3] (2-CNS) which, upon dmpe addition, yields [Fe(CNS)(PMe3)(dmpe)] (3-CNS). Treatment of the previously reported cationic Fe amine-amido complex [Fe(SMeNHSMe)(SMeNSMe)]+ with PMe3 gave FeII aryl-imine-thioether complex [Fe(CNSMe)(PMe3)3]+ (4-CNS′) via selective activation of both Caryl–S and benzylic C–H bonds. Assessment of complexes 3-CNS, 4-SNS, and 4-CNS′ as precatalysts for amine-borane dehydrogenation catalysis in THF at 60 °C shows that 3-CNS forms a selective and robust bifunctional catalyst system.
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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 | 0.001 |
| 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) | 0.000 | 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".