Dithiophosphinates of gold (I); oxidative addition of Cl<sub>2</sub> to a neutral, dinuclear gold(I) dithiophosphinate complex, and X-ray crystal structures of [AuS<sub>2</sub>P(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>]<sub>2</sub>, [AuS<sub>2</sub>PPh<sub>2</sub>]<sub>2</sub>, Au<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>PMe<sub>2</sub>(S<sub>2</sub>PPh<sub>2</sub>), and Au<sub>2</sub>Cl<sub>2</sub>[(CH<sub>2</sub>)<sub>2</sub>PMe<sub>2</sub>][S<sub>2</sub>PPh<sub>2</sub>]
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Bibliographic record
Abstract
The formation and characterization of dinuclear gold(I) dialkyl- and diaryl-dithiophosphinate complexes of the type [AuS 2 PR 2 ] 2 are described. The complexes are readily prepared from the reaction between a chlorogold(I) starting material and the corresponding dithiophosphinate salt. The structures of the complexes show both the absence (R = Et, 1) and presence (R = Ph, 2a) of intermolecular Au···Au interactions as confirmed by X-ray crystallographic study in the solid state. Reaction between [AuS 2 PPh 2 ] 2 and [Au(CH 2 ) 2 PMe 2 ] 2 in CH 2 Cl 2 solution leads to a ligand transfer reaction to form the hetero-bridged complex [Au 2 {(CH 2 ) 2 PMe 2 S 2 PPh 2 }] (3a) in high yield. Additionally, the latter complex reacts with Cl 2 to form the oxidative addition product [Au 2 Cl 2 {(CH 2 ) 2 PMe 2 S 2 PPh 2 }] (4), the first gold(II) complex with a S-P-S bridging moiety. The X-ray crystal structure of both 3a and 4 exhibit rare boat conformations in the solid state, and 4 has a formal Au(II)Au(II) single bond of 2.5611(5) Å. Reaction between [AuS 2 PPh 2 ] 2 and dppm (dppm = Ph 2 PCH 2 PPh 2 ) leads to a sparsely soluble three-coordinate dinuclear gold(I) complex with the molecular formula [Au 2 {dppmS 2 PR 2 } 2 ] n (n = 1 or [Formula: see text]) (5).Key words: dithiophosphinates, ylide, dithiols, gold-gold bond.
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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 | 0.027 | 0.017 |
| Meta-epidemiology (narrow) | 0.052 | 0.061 |
| Meta-epidemiology (broad) | 0.049 | 0.029 |
| Bibliometrics | 0.028 | 0.041 |
| Science and technology studies | 0.021 | 0.029 |
| Scholarly communication | 0.017 | 0.029 |
| Open science | 0.035 | 0.019 |
| Research integrity | 0.035 | 0.049 |
| Insufficient payload (model declined to judge) | 0.001 | 0.007 |
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