Synthesis, structural characterization, and reactivity of (thiolato)bismuth complexes as potential water-tolerant Lewis acid catalysts
Why this work is in the frame
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Bibliographic record
Abstract
We have synthesized bismuth complexes incorporating polydentate mono- and di-thiolate ligands and examined their utility as water-tolerant Lewis acid catalysts. The reaction of Bi(OAc) 3 or Bi(NO 3 ) 3 ·5H 2 O and the corresponding mono- or di-thiol(ate) yielded the compounds [(SNNS)Bi(OAc)] (4), [(SNNSPr)Bi(OAc)] (5), [(NNS 2 )Bi(OAc)] (6), [(ONS 2 )Bi(OAc)] (7), [(ONS 2 )Bi(NO 3 )] (8), and [(NNS) 2 Bi][NO 3 ] (9) [H 2 (SNNS) = N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)ethylenediamine; H 2 (SNNSPr) = N,N′-diethyl-N,N′-bis(2-mercaptoethyl)propanediamine; H 2 (NNS 2 ) = N,N-diethyl-N′,N′-bis(2-mercaptoethyl)ethanediamine; H 2 (ONS 2 ) = 2-methoxyethyl-bis(2-mercaptoethyl)amine; H(NNS) = N,N-diethyl-N′-(2-mercaptoethyl)ethanediamine]. The solid-state structures of 4–8 show similar distorted pentagonal pyramidal geometries at the bismuth centre with a thiolate sulfur atom in the axial site, whereas 8 shows second structural arrangement with a distorted trigonal bipyramidal geometry at bismuth. The cation of 9 shows two NNS-bonded ligands and a distorted octahedral geometry at bismuth. Two-dimensional NMR studies of 4–8 show geminal 1 H coupling in –SCH 2 CH 2 N– groups and suggests strong dative Bi–N intramolecular interactions. Bi(NO 3 ) 3 ·5H 2 O and BiCl 3 show high activity toward the esterification of stearic acid, Bi(NO 3 ) 3 ·5H 2 O, and 4–7 and 9 show high activity toward the transesterification of methyl stearate in butanol, and 7 shows moderate activity as a catalyst for the transesterification of glyceryl trioctanoate in methanol.
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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 | 0.000 |
| 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) | 0.003 | 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 it