Rh and Ir β-Diiminate Complexes of Boranes, Silanes, Germanes, and Stannanes
Bibliographic record
Abstract
Reported here are several new adducts of the type ( R BDI)M(HE) 2 where R BDI is the β-diiminate ligand [2,6-R 2 C 6 H 3 N═CMe] 2 CH (R = Me, Et, MeO; M = Rh, Ir; HE = HSiEt 3, HGeEt 3, HSn n Bu 3, HBPin). DFT calculations are used to analyze the bonding in these and related Cp* complexes, in particular with respect to the degree of oxidative addition (OA) of the H–E bonds: this increases in the order H 2 < HBPin < HSiEt 3 ≈ HGeEt 3 ≈ HSn n Bu 3, it proceeds further for Ir than for Rh, and Cp* promotes OA to a larger degree in comparison to the BDI ligand. The first metal–HE dissociation energy is rather sensitive to steric effects and increases in the order CH 4 ≪ H 2 ≈ HBPin ≈ HSiMe 3 ≈ HGeMe 3 < HSnMe 3, with Ir uniformly binding HE more strongly than Rh by about 10 kcal/mol. M–HE dissociation is the first step of the intramolecular ligand functionalization first reported for ( Me BDI)Rh(HSiEt 3 ) 2 . Such functionalization was not observed for any of the new complexes reported here. On the basis of the idea that stannane dissociation might be prohibitive, we obtained evidence that it is possible to effect such functionalization via generation of a stannane within the coordination sphere of the metal: treatment of ( Me BDI)Rh(COE)(N 2 ) with SnMe 4 and H 2 produced a mixture of ( Me BDI)Rh(HSnMe 3 ) 2 and its functionalized derivative ( Me BDI∧SnHMe 2 )Rh(HSnMe 3 ) via Sn–C cleavage.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.006 | 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".