Synthesis and reactivity of low-coordinate diamagnetic Rh and Ir complexes and paramagnetic Rh(II) complexes
Bibliographic record
Abstract
Low-coordinate complexes generally show high reactivity and the lower the coordination number is, the higher the reactivity would be. Oxidative addition of C-H and X-H bonds is one of the most important and basic steps in organometallic catalysis. In this work, oxidative addition of Si-H, Sn-H and B-H bonds (E-H) at low-coordinate Rh and Ir β-diiminate (BDI) complexes to form dihydride and trihydride complexes are described. In addition, ligand functionalization via a cleavage of an Sn-C bond was obtained by the treatment of (MeBDI)Rh(COE)(N2) (MeBDI = (2,6-Me2C6H3N=CMe)2CH) with SnMe4 and H2. Steric effects are significant controlling the reactions with EH substrates. To explore the limits of steric hindrance, reaction of (MeBDI)Rh(COE)(N2) with bulky PPh3 was tested, leading to a complex containing a tautomerized BDI ligand. Paramagnetic complexes of platinum group metals often show high and radical-like reactivity. They have one or more single electrons which typically show wide and broad peaks on NMR and they are usually characterized by EPR. Starting from [(MeBDI)Rh]2(μ-Br)2, low-coordinate monomeric Rh(II) complex (MeBDI)Rh(2,6-iPr2C6H3NH) was successfully isolated through reaction with lithium 2,6-diisopropylanilide. Reactions with less hindered anilides resulted in eventual formation of diamagnetic final products. Reactions of [(MeBDI)Rh]2(μ-Br)2 with lithium 2,6-dimethylanilide involves benzylic C-H activation while C-N coupling is observed with unsubstituted lithium anilide.
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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) | 0.001 | 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".