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 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 | 0.001 |
| 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 | 0.001 | 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 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".