Stoichiometric and Catalytic Oxidation of BINAP by Dioxygen in a Rhodium(I) Complex
Bibliographic record
Abstract
The square planar complex (BINAP)Rh(CO)Cl (BINAP = 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl) was synthesized from [Rh(COD)Cl] 2 (COD = 1,5 cyclooctadiene) and BINAP under a CO atmosphere. It reacts with oxygen to form the square planar (BINAP(O))Rh(CO)Cl in approximately 50% yield, along with molar equivalents of free BINAP dioxide (BINAP(O) 2 ) and CO 2 . The oxygen atom of the BINAP(O) was shown crystallographically to be trans to the CO ligand. In the presence of excess BINAP under CO/O 2 gas mixtures, the reaction is catalytic with a TOF of 0.16 h - 1 at ambient temperature in chloroform. The kinetics of this transformation were investigated and conditions for optimum selectivity for BINAP(O) formation suggested. A stoichiometric mechanism is proposed that involves initial formation of an O 2 adduct, followed by oxygen atom transfer to both phosphorus atoms of BINAP or to one phosphorus atom and the CO ligand trans to it. These processes might be concerted, or stepwise with intermediate Rh O species. To the best of our knowledge, this chemistry represents the first example of a reaction exhibiting oxygen atom addition from O 2 either to both phosphorus atoms in a bisphosphine ligand or to one phosphorus atom and a CO ligand in the same complex.
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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 | 0.001 | 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 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".