Accessing δ-B–H Coordinated Complexes of Rh(I) and Ir(I) Using Mono- and Dihydroboranes: Cooperative Stabilization by a Phosphoramidate Coligand
Bibliographic record
Abstract
Reactions of the four-membered irida(I)- and rhoda(I)heterocycles [M{κ 2 - N, O - Xyl( N )P( O )(OEt) 2 }(η 4 -COD)] (M = Rh ( 1 ), Ir ( 2 )) with electrophilic borane reagents are investigated. Treatment of 1 or 2 with 9-borabicyclo[3.3.1]nonane (HBC 8 H 14 ) gives [M{κ 2 - N, H -Xyl( N )P(O H (BC 8 H 14 ) ( OEt) 2 }(η 4 -COD)] (M = Rh ( 5 ), Ir ( 6 )). Complexes 1 and 2 display differing reactivity toward HBMes 2 and H 2 BMes: reaction with HBMes 2 provides an equilibrium mixture of [M{κ 2 - N, H - Xyl( N )P(O H B(Mes) 2 )(OEt) 2 }(η 4 -COD)] (M = Rh ( 7 ), Ir ( 8 )) and the precursor complex 1 or 2 . For H 2 BMes, borane coordination was found to be irreversible and the five-coordinate bis(B–H) complexes [M{κ 3 - N,H,H - Xyl( N )P(O H 2 BMes)(OEt) 2 }(η 4 -COD)] (M = Rh ( 9 ), Ir ( 10 )) were accessed. Complexes 9 and 10 are highly fluxional in solution; this is ascribed to rapid rotation of the 1,5-cyclooctadiene (COD) coligand. Treatment of 1 or 2 with Piers’ borane, HB(C 6 F 5 ) 2, also provides the corresponding ring-expanded metalla(I)cycles [M{κ 2 - N, H - Xyl( N )P(O H B(C 6 F 5 ) 2 )(OEt) 2 }(η 4 -COD)] (M = Rh ( 11 ), Ir ( 12 )). In the absence of a stabilizing [M]··H–B interaction, treatment of 1 or 2 with B(C 6 F 5 ) 3 provides the corresponding η 5 -iminocyclohexadienyl complexes [M{η 5 -Xyl(N)P(O··B(C 6 F 5 ) 3 )(OEt) 2 }(η 4 -COD)] (M = Rh ( 21 ), Ir ( 22 )), which result from phosphine oxide donation to the electron-deficient boron center.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 | 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".