Reactivity of an Unsaturated Iridium(III) Phosphoramidate Complex, [Cp*Ir{κ<sup>2</sup>-<i>N</i>,<i>O</i>}][BAr<sup>F</sup><sub>4</sub>]
Bibliographic record
Abstract
The three-legged piano stool complex [Cp*Ir(κ 2 - N, O -Xyl( N )P( O )(OEt) 2 )(Cl)], [ 1 ] (Cp* = η 5 -C 5 Me 5, Xyl = 2,6-dimethylphenyl), was prepared from reaction of 0.5 equiv of [Cp*IrCl 2 ] 2 with the sodiated phosphoramidate ligand Na[Xyl(N)P(O)(OEt) 2 ]. Treatment of [ 1 ] with Na[BAr F 4 ], [BAr F 4 ] = [B(C 6 H 3 (CF 3 ) 2 ) 4 ], led to the formation of the 16-electron two-legged piano stool species [Cp*Ir(κ 2 - N, O -Xyl( N )P( O )(OEt) 2 )][BAr F 4 ], [ 2 ][BAr F 4 ], which was characterized in both solution and solid state. Reactivity screening revealed that complex [ 2 ][BAr F 4 ] undergoes addition of a variety of Lewis bases to afford the corresponding 18-electron adducts with concomitant movement of the phosphoramidate ligand from κ 2 - N, O to κ 1 - N, [Cp*Ir(κ 1 - N -Xyl( N )P(O)(OEt) 2 )(L) 2 ][BAr F 4 ]; L = CN t Bu, [ 3 ][BAr F 4 ], CNXyl, [ 4 ][BAr F 4 ], MeCN, [ 7 ][BAr F 4 ], bipy, [ 8 ][BAr F 4 ]; bipy = 2,2′-bipyridine. For complex [ 7 ][BAr F 4 ], variable-temperature 31 P{ 1 H} NMR spectroscopy revealed that MeCN coordination was reversible between 238 and 190 K. To probe E–H (E = Si, B) bond activation, complex [ 2 ][BAr F 4 ] was treated with H 2 SiPh 2, providing the five-membered iridacycle [Cp*Ir(κ 2 - N,Si -Xyl( N )P(O Si Ph 2 )(OEt) 2 )][BAr F 4 ], [ 9 ][BAr F 4 ], via geminal Si–H activation, while use of mesityl borane, H 2 BMes (Mes = 2,4,6-trimethylphenyl), afforded the six-membered phosphoramidate-stabilized borane complex [Cp*Ir(κ 3 - N,H,H -Xyl( N )P(OB H 2 Mes)(OEt) 2 )][BAr F 4 ], [ 10 ][BAr F 4 ]. Complexes [ 3 ][BAr F 4 ] and [ 9 ][BAr F 4 ] were additionally characterized by single-crystal X-ray diffraction.
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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) | 0.002 | 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 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".