Mono- and bis-(acetylacetonato) complexes of arene-ruthenium(II) and arene-osmium(II): variation of the binding mode of η<sup>1</sup>-acetylacetonate with the nature of the arene
Bibliographic record
Abstract
The mono(acetylacetonato) complexes [MCl(O,O'-acac)(η 6 -arene)] (M = Ru, Os, arene = C 6 H 6 , 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 ; M = Os, arene = 1,2-C 6 H 4 Me 2 , 1,2,3-C 6 H 3 Me 3 ), which are formed from [MCl 2 (η 6 -arene)] 2 and thallium or sodium acetylacetonate, react with thallium acetylacetonate to give bis(acetylacetonato) complexes [M(O,O'-acac)(η 1 -acac)(η 6 -arene)]. The η 1 -acac ligand is bound through the gamma-carbon atom for M = Ru, Os, arene = C 6 H 6 ; M = Os, arene = 1,2-C 6 H 4 Me 2 , 1,2,3-C 6 H 3 Me 3 and through a keto-oxygen atom for M = Ru, Os, arene = 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 , the difference being attributed to a combination of steric and electronic effects. Cationic ruthenium(II) derivatives [Ru(L)(O,O'-acac)(η 6 -arene] + (arene = C 6 H 6 , 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 ; L = DMSO, MeCN, py, PPh 3 ) and [Ru(CO)(O,O'-acac)(η 6 -arene] + (arene = 1,3,5-C 6 H 3 Me 3 ,C 6 Me 6 ), and neutral osmium(II) η 1 -acetato derivatives [Os(η 1 -OAc)(O,O'-acac)(η 6 -arene)] (arene = C 6 H 6 , 1,2-C 6 H 4 Me 2 , 1,2,3-C 6 H 3 Me 3 , 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 ) are also described. The molecular structures of the following complexes have been determined by X-ray crystallography: [Os(O,O'-acac)(η 1 -C-acac)(η 6 -1,2-C 6 H 4 Me 2 )], triclinic, space group P[Formula: see text] (No. 2), a = 9.922(2), b = 9.974(2), and c = 11.001(2) Å, α = 68.33(1), β = 64.18(1), and γ = 62.38(1)°, V = 849.0(3) Å 3 , Z = 2; [Os(O,O'-acac)(η 1 -O-acac)(η 6 -1,3,5-C 6 H 3 Me 3 )], monoclinic, space group C2/c (No. 15), a = 16.032(4), b = 11.989(3), and c = 21.562(7) Å, β= 108.91(2)°, V = 3921(2) Å, Z = 8; [Os(η 1 -OAc)(O,O'-acac)(η 6 -C 6 H 6 )], triclinic, space group P[Formula: see text] (No. 2), a = 8.368(4), b = 8.402(4), and c = 11.008(4) Å, α = 71.68(3), β = 69.35(3), and γ = 69.77(3)°, V = 663.0(6) Å 3 , Z = 2.Key words: arene-ruthenium, arene-osmium, acetylacetone, crystal structures.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".