Cationic, Neutral, and Anionic Hydrides of Iridium with PSiP Pincers
Bibliographic record
Abstract
This work describes synthetic routes from the known precursor [IrClH{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }] ( 1 ) to new hydride and polyhydride derivatives. Substituting the chloride ligand with triflate leads to the five-coordinate complex [IrH{κ O -O 3 S(CF 3 )}{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }] ( 2 ), which can undergo reversible coordination of water (H 2 O) or dihydrogen (H 2 ) to generate respectively the cationic derivative [IrH{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }(OH 2 ) 2 ](CF 3 SO 3 ) ( 3 ) or the neutral trans -hydride–dihydrogen [IrH{κ O -O 3 S(CF 3 )}{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }(η 2 -H 2 )] ( 6 ) in equilibrium. The use of acetonitrile or carbon monoxide (CO) excess instead of water produces stable analogues of 3 (complexes 4 or 5, respectively). The reaction between 1 and NaBH 4 affords the tetrahydroborate derivative [IrH{κ 2 H -H 2 BH 2 }{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }] ( 7 ), which can be protonated with triflic acid to form 2 or with HBF 4 to give the dinuclear cationic derivative [(μ:κ 2 H,κ 2 H -BH 4 )[IrH{κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }] 2 ](BF 4 ) ( 8 ). The reactions of 7 with alcohols afford either the dihydride–carbonyl [IrH 2 {κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }(CO)] ( 9 ) or the known tetrahydride [IrH 4 {κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }] ( 10 ), depending on the ease of alcohol decarbonylation. NMR observations and density functional theory calculations on the fluxional behavior of 10 indicate that the spatial contour of the mer PSiP framework conditions hydride-ligand exchanges. Complex 10 reacts with NaH in tetrahydrofuran to form the anionic trihydride [IrH 3 {κ P, P, Si -Si(Me)(C 6 H 4 -2-P i Pr 2 ) 2 }]Na ( 11 ), which exists as a mixture of fac and mer isomers in equilibrium.
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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".