Binding of CO and NH3 at a five-coordinate Ru(ii) centre in the solid state and in solution
Bibliographic record
Abstract
The known five-coordinate, square-pyramidal, green trans-RuCl2(P-N)(PR3) complexes (P-N = o-diphenylphosphino-N,N'-dimethylaniline; R = Ph (1a), p-tolyl), in the solid state at ambient conditions, or in CDCl3 solution at low temperatures, coordinate CO (at 1 atm) to form beige-coloured trans-monocarbonyl derivatives. In the solution reactions at room temperature, the PR3 ligand dissociates and the yellow dicarbonyl complex RuCl2(CO)2(P-N) is formed as a mixture of trans,cis- and cis,cis-isomers. With use of (13)CO, the carbonyls complexes are characterized by variable temperature NMR and IR data, and (for the monocarbonyls) elemental analyses. Similarly, 1a and the dibromo analogue (1b) in the solid state bind NH3 to form the beige trans-monoammine species RuX2(P-N)(PPh3)(NH3), trans-4a (X = Cl) and trans-4b (X = Br), with cis P-atoms. The solution NH3 reactions, however, generate a species, speculatively thought to be the unusual, tight ion-pair, bisammine species [RuX(P-N)(PPh3)(NH3)2···X], 5a (X = Cl) and 5b (X = Br), in which a halide is considered strongly H-bonded to the cis-ammine ligands, although an alternative RuX(P-N)(PPh3)(NH3)2 formulation with a monodentate P-N ligand cannot be ruled out; dissolution in CDCl3 of isolated 5a and 5b, which are characterized by NMR, elemental analysis, and conductivity data, results in a partial, reversible loss of NH3 to form some cis- and trans-4a or -4b, respectively. Treatment of 5a with one mole equivalent of NH4PF6 in acetone solution removes the H-bonded chloride to give [RuCl(P-N)(PPh3)(NH3)2]PF6 (6), and this is converted by thermal loss of NH3 to generate the extremely air-sensitive, five-coordinate, ionic species [RuCl(P-N)(PPh3)(NH3)]PF6 (7). NMR evidence is presented for formation of the tris(ammine) species [Ru(P-N)(PPh3)(NH3)3](PF6)2 (8) via treatment of trans-RuCl2(P-N)(PPh3) with an atmosphere of NH3 in the presence of 2 mole equivalents of NH4PF6.
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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".