Interaction of SbCl<sub>5</sub><sup>2−</sup> and Thioether Groups at the Open Coordination Sites of Platinum(II) Diimine Complexes
Bibliographic record
Abstract
In the solid-state, the approximately square planar cation in orange crystals of [Pt(NO(2)phen)(ttcn)](PF(6))(2) (NO(2)phen = 5-nitro-1,10-phenanthroline; ttcn = 1,4,7-trithiacyclononane) has a short apical Pt...S(ttcn) distance (2.9415(15) A). In acetonitrile solution, the electronic spectrum shows a long-wavelength absorption band (412 nm; 2200 M(-1) cm(-1)), consistent with the notion that the axial Pt...S(ttcn) interactions stabilize states having metal-to-ligand charge-transfer (MLCT) character. Reaction with the hexachloroantimonate(V) salt of tris(4-bromophenyl)aminium (TBPA(+)) results in complex redox chemistry, involving the platinum complex, SbCl(5)(2-) and TBPA(+). In the case of Pt(bpy)(ttcn)(2+), orange-yellow crystals of [Pt(bpy)(ttcn)](2)(Sb(4)Cl(16)) were isolated from the reaction, whereas the reaction with Pt(NO(2)phen)(ttcn)(2+) consistently yielded red crystals of [Pt(NO(2)phen)(ttcn)](SbCl(5)) x 2 CH(3)CN. In the latter case, the geometry of the cation, including the apical Pt...S(ttcn) distance (2.9390(12) A), is very similar to that of the PF(6)(-) salt. However, the basal plane of each square pyramidal SbCl(5)(2-) opposes the nearly parallel coordination plane of an adjacent Pt(NO(2)phen)(ttcn)(2+) complex, resulting in an unusually short intermolecular Pt...Sb distance of 3.4259(3) A. The longest wavelength maximum in the diffuse reflectance spectrum and the solid-state emission maximum are shifted by approximately 1200 cm(-1) and approximately 700 cm(-1), respectively, to the red of those of the PF(6)(-) salt, consistent with perturbation of the complex's electronic structure because of the Pt...Sb interaction.
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How this classification was reachedexpand
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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".