Phosphine-Substituted Dithiolene Complexes as Ligands: Communication between Ruthenium(II) Centers Through a Dimolybdenum Bis(dithiolene) Core
Bibliographic record
Abstract
The reaction of Mo2(SCH2CH2S)2Cp2 (1; Cp=eta-C5H5) with an excess of an alkyne in refluxing dichloromethane affords the bis(dithiolene) complexes Mo2(micro-SCR1=CR2S)2Cp2 (2a, R1=R2=CO2Me; 2b, R1=R2=Ph; 2c, R1=H, R2=CO2Me) whereas with 1 equiv of alkyne at room temperature the mixed dithiolene-dithiolate species Mo2(micro-SCR1=CR2S)(micro-SCH2CH2S)Cp2 (3a, R1=R2=CO2Me; 3b, R1=R2=Ph) are formed. The remaining dithiolate ligand in 3 can then be converted into a different dithiolene by reaction with a second alkyne. Applying this methodology, we have used bis(diphenylphosphino)acetylene to prepare the first examples of complexes containing phosphine-substituted dithiolene ligands: Mo2{micro-SC(CO2Me)=C(CO2Me)S}{micro-SC(PPh2)=C(PPh2)S}Cp2 (2g) and Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2 (2h). Tri- and tetrametallic complexes can then be assembled by coordination of these diphosphines to CpRuCl units by reaction with CpRu(PPh3)2Cl. Electrochemical studies of the Ru(II)/Ru(III) couple in Mo2{micro-SC(PPh2)=C(PPh2)S}2Cp2(RuClCp)2 (4b) reveals that the two separate ruthenium centers are oxidized electrochemically at different potentials, demonstrating communication between them through the dimolybdenum bis(dithiolene) core. Density functional theory calculations were carried out to explore the electronic structures of these species and to predict and assign their electronic spectra.
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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 | 0.000 |
| 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 | 0.001 |
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".