Iron(II) Complexes of a Hemilabile SNS Amido Ligand: Synthesis, Characterization, and Reactivity
Bibliographic record
Abstract
We report an easily prepared bis(thioether) amine ligand, S Me N H S Me, along with the synthesis, characterization, and reactivity of the paramagnetic iron(II) bis(amido) complex, [Fe(κ 3 -S Me NS Me ) 2 ] ( 1 ). Binding of the two different thioethers to Fe generates both five- and six-membered rings with Fe–S bonds in the five-membered rings (av 2.54 Å) being significantly shorter than those in the six-membered rings (av 2.71 Å), suggesting hemilability of the latter thioethers. Consistent with this hypothesis, magnetic circular dichroism (MCD) and computational (TD-DFT) studies indicate that 1 in solution contains a five-coordinate component [Fe(κ 3 -S Me NS Me )(κ 2 -S Me NS Me )] ( 2 ). This ligand hemilability was demonstrated further by reactivity studies of 1 with 2,2′-bipyridine, 1,2-bis(dimethylphosphino)ethane, and 2,6-dimethylphenyl isonitrile to afford iron(II) complexes [L 2 Fe(κ 2 -S Me NS Me ) 2 ] ( 3 – 5 ). Addition of a Brønsted acid, HNTf 2, to 1 produces the paramagnetic, iron(II) amine–amido cation, [Fe(κ 3 -S Me NS Me )(κ 3 -S Me N H S Me )](NTf 2 ) ( 6; Tf = SO 2 CF 3 ). Cation 6 readily undergoes amine ligand substitution by triphos, affording the 16e – complex [Fe(κ 2 -S Me NS Me )(κ 3 -triphos)](NTf 2 ) ( 7; triphos = bis(2-diphenylphosphinoethyl)phenylphosphine). These complexes are characterized by elemental analysis; 1 H NMR, Mössbauer, IR, and UV–vis spectroscopy; and single-crystal X-ray diffraction. Preliminary results of amine–borane dehydrogenation catalysis show complex 7 to be a selective and particularly robust precatalyst.
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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 | 0.000 | 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 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".