Mechanistic study of ligand substitution processes in TpIr(III) complexes
Bibliographic record
Abstract
The synthesis of the cationic hydridotris(pyrazolyl)borate iridium(III) complex [Tp(PMe 3 )IrMe(ClCH 2 Cl)][BAr f ] (2-CH 2 Cl 2 ) is reported. Spectroscopic characterization of 2-CH 2 Cl 2 in CH 2 Cl 2 solution indicates that exchange of bound CH 2 Cl 2 with free CH 2 Cl 2 is slow on the NMR time scale. Under 50 atm (1 atm = 101.325 kPa) of N 2 , the CH 2 Cl 2 in 2-CH 2 Cl 2 is displaced by N 2 to yield [Tp(PMe 3 )IrMe(N 2 )][BAr f ] (2-N 2 ). The stronger nucleophile CH 3 CN reacts rapidly with 2-CH 2 Cl 2 to produce [Tp(PMe 3 )IrMe(NCCH 3 )][BAr f ] (4). A kinetic study was performed on CH 2 Cl 2 substitution in 2-CH 2 Cl 2 by CD 3 CN. The data are most consistent with dissociative loss of CH 2 Cl 2 to generate the unsaturated species ([Tp(PMe 3 )IrMe][BAr f ]) which then reacts with CD 3 CN to generate [Tp(PMe 3 )IrMe(NCCD 3 )][BAr f ]. Further evidence for a dissociative mechanism was obtained by comparison of ligand substitution rates for the Tp complexes with the analogous Tp Me2 complexes (Tp Me2 = hydridotris(3,5-dimethylpyrazolyl)borate). The relevance of these substitution experiments to CH activation by cationic iridium(III) complexes is discussed.Key words: iridium, hydridotris(pyrazolyl)borate, methylene chloride and dinitrogen complexes, dissociative substitution.
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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) | 0.006 | 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".