Bond Stretching and Redox Behavior in Coinage Metal Complexes of the Dichalcogenide Dianions [(SPh<sub>2</sub>P)<sub>2</sub>CEEC(PPh<sub>2</sub>S)<sub>2</sub>]<sup>2−</sup> (E=S, Se): Diradical Character of the Dinuclear Copper(I) Complex (E=S)
Bibliographic record
Abstract
The metathetical reactions of a) [Li(tmeda)](2)[(S)C(PPh(2)S)(2)] (Li(2)·3c) with CuCl(2) and b) [Li(tmeda)](2)[(SPh(2)P)(2)CSSC(PPh(2)S)(2)] (Li(2)·4c) with two equivalents of CuCl both afford the binuclear Cu(I) complex {Cu(2)[(SPh(2)P)(2)CSSC(PPh(2)S)(2)]} (5c). The elongated (C)S-S(C) bond (ca. 2.54 and 2.72 Å) of the dianionic ligand observed in the solid-state structure of 5c indicate the presence of diradical character as supported by theoretical analyses. The treatment of [Li(tmeda)](2)[(SPh(2)P)(2)CSeSeC(PPh(2)S)(2)] (Li(2)·4b) and Li(2)·4c with AgOSO(2)CF(3) produce the analogous Ag(I) derivatives, {Ag(2)[(SPh(2)P)(2)CEEC(PPh(2)S)(2)]} (6b, E=Se; 6c, E=S), respectively. The diselenide complex 6b exhibits notably weaker Ag-Se(C) bonds than the corresponding contacts in the Cu(I) congeners, and the (31)P NMR data suggest a possible isomerization in solution. In contrast to the metathesis observed for Cu(I) and Ag(I) reagents, the reactions of Li(2)·4b and Li(2)·4c with Au(CO)Cl involve a redox process in which the dimeric dichalcogenide ligands are reduced to the corresponding monomeric dianions, [(E)C(PPh(2)S)(2)](2-) (3b, E=Se; 3c, E=S), and one of the gold centers is oxidized to generate the mixed-valent Au(I)/Au(III) complexes, {Au[(E)C(PPh(2)S)(2)]}(2) (7b, E=Se; 7c, E=S), with relatively strong aurophilic Au(I)···Au(III) interactions. The new compounds 5c, 6b,c and 7b,c are characterized in solution by NMR spectroscopy and in the solid state by X-ray crystallography (5c, 6b, 7b and 7c) and by Raman spectroscopy (5c and 6c). The UV-visible spectra of coinage metal complexes of the type 5, 6 and 7 are discussed in the light of results from theoretical analyses using time-dependent density functional theory.
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) | 0.002 | 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 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".