Synthesis, electrochemistry, and reactivity of bismuth(III) and indium(III) dithiolene complexes
Bibliographic record
Abstract
Bismuth(III) and indium(III) compounds of redox-active dithiolene ligands were synthesized and their electrochemical properties and reactivity investigated. The 1:1 reaction of MesMgBr (Mes = 2,4,6-trimethylphenyl) and ClBi(tdt) [(tdt) 2− = 3,4-toluenedithiolate] afforded a mixture of products that included (Mes 2 Bi) 2 (tdt) (1), which was subsequently isolated from the 2:1 reaction of Mes 2 BiCl and Li 2 (tdt). The 1:2 reaction of BiCl 3 and Na 2 (tdt), followed by addition of one equivalent of NEt 4 Cl or NBu 4 Cl, resulted in formation of [NEt 4 ][(tdt) 2 Bi] (2) or [NBu 4 ][(tdt) 2 Bi] (3), respectively. Alternatively, the 1:2 reaction of Na 2 (mnt) (mnt 2− = maleonitrileditholate) and InCl 3 , followed by addition of one equivalent of NEt 4 Cl, resulted in formation of [NEt 4 ] 2 [(mnt) 2 InCl] (4). The solid-state structures of 1, 3, 4, and ClBi(tdt)(py) 2 (5) were determined by X-ray crystallography. CV studies of 2 and 4 show that both compounds undergo decomposition upon electrochemical oxidation. Reaction of 2 with I 2 or MeI resulted in formation of [tdt] n (6) or Me 2 (tdt) (7), respectively, and [NEt 4 ] 3 [Bi 3 I 12 ] (8). The reaction of 4 with I 2 and MeI resulted in formation of tetracyano-1,4-dithiin (9) and Me 2 (mnt) (11), respectively, and [NEt][InI 4 ] (10). DFT computational studies were carried out to discern the electrochemical properties and reactivity of compounds 2 and 4. This study highlights the high and unpredictable reactivity of bismuth and indium dithiolenes, and demonstrates their potential as precursors for novel 1,2,5,6-tetrathiocins and higher oligomers, 1,4-dithiins, and methylated dithiolenes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 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".