Experimental and Theoretical Investigations of Tellurium(IV) Methanediides and Their Insertion Products with Sulfur and Iodine
Bibliographic record
Abstract
The reactions of Li 2 [C(Ph 2 PS) 2 ] with tellurium tetrahalides in a 1:1 molar ratio in toluene afford the complexes {TeX 2 [C(Ph 2 PS) 2 ]} 2 ( 7a, X = Cl; 7b, X = Br; 7c, X = I). These complexes dimerize through halide bridges in the solid state, and the tridentate ligand is S,C,S- coordinated to the tellurium center with a Te–C bond length of 2.024(3), 2.030(6), and 2.045(8) Å, respectively. In the case of TeBr 4, small amounts of the complex TeX 2 [SC(Ph 2 PS) 2 ] ( 8b, X = Br) were isolated and shown by X-ray analysis to be the result of formal sulfur insertion into the Te–C bond of 7b . Complex 8b and the corresponding dichloride and diiodide, 8a (X = Cl) and 8c (X = I), may be prepared in good yields by the metathetical reactions of Li 2 [SC(Ph 2 PS) 2 ] with TeX 4 in toluene. The complex TeI 2 [(I 2 )C(Ph 2 PS) 2 ] ( 9 ) was isolated as a minor product from the reaction of Li 2 [C(Ph 2 PS) 2 ] and TeI 4 and identified by X-ray crystallography. Complex 9 is constructed from the insertion of an iodine atom of an I 2 molecule into the Te–C bond of 7c, resulting in a T-shaped geometry at that iodine atom and an almost linear Te–I–I unit with an elongated I–I bond; the C–I bond length is typical for a C(sp 3 )–I bond. DFT calculations supplemented with Hirshfeld charge analysis, Boys–Foster localization of molecular orbitals, and evaluation of the electron localization functions indicate that in these species the ligand engages predominantly in σ bonding through the lone pairs on the carbon and sulfur atoms. The latter atoms participate in three-center interactions with tellurium. The bonds between the heavy elements and carbon are strongly polarized, and the character of the latter atom ranges from sp 2 to sp 3 .
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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 | 0.001 |
| 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) | 0.006 | 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".