A Structural Investigation of Dimethylthallium(III) Thiolate and Selenolate Rings and Polymers
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Bibliographic record
Abstract
Abstract The effects of increased steric bulk in dimethylthallium(III) chalcogenolates on oligomerization was examined. The facile reaction of Me 3 Tl with a series of benzenethiols and ‐selenols in toluene or thf resulted in the formation of [Me 2 TlS(2,6‐Me 2 C 6 H 3 )] ∞ ( 2 ), [Me 2 TlS(2,4,6‐ t Bu 3 C 6 H 2 )] ∞ ( 3 ), [Me 2 TlSe(C 6 H 5 )] 2 ( 4 ), [Me 2 TlSe(2,4,6‐Me 3 C 6 H 2 )] ∞ ( 5 ), and [Me 2 TlSe(2,4,6‐ t Bu 3 C 6 H 2 )] ∞ ( 6 ). The solid‐state structure of 4 is dimeric with short intermolecular Tl ··· Se interactions, which yields an asymmetric Tl 2 Se 2 core and a distorted tetrahedral C 2 Se 2 bonding environment for the thallium. The increase in the steric bulk of the chalcogenolate ligand in compounds 2 and 5 results in the formation of polymeric structures with μ‐E[2,(4),6‐Me 3 C 6 H 2 ] (E = S, Se) groups and distorted tetrahedral C 2 E 2 bonding environments for the thallium. A further increase in the steric bulk of the phenylchalcogenolate resulted in the formation of chains of weakly coordinated monomers by means of the intermolecular Tl ··· E interactions in 3 (E = S) and 6 (E = Se). This work represents the first systematic study of diorganothallium thiolates and selenolates and compounds 4 – 6 represent the first structurally characterized examples of R 2 TlSeR′ species. A comparison of the structures of [Me 2 TlS(C 6 H 5 )] 2 ( 1 ) and 2 – 6 with other group 13 analogue structures suggests that the degree of oligomerization differs for [Me 2 MSR′] n (M = Tl) versus the analogous (M = Al, Ga, and In) species. These findings areimportant in understanding the factors that govern oligomerization (i.e. ring size) and polymerization of diorganotriel chalcogenolates.
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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) | 0.001 | 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 it