Synthesis of New Late Transition Metal P,P-, P,N-, and P,O- Complexes Using Phosphonium Dimers as Convenient Ligand Precursors
Bibliographic record
Abstract
The phosphonium dimer [-Cy2PCH(OH)CH2-]2(X)2, X = Cl(-), Br(-) was used to synthesize and characterize a variety of late transition metal complexes containing chelating phosphino-enolate (PCy2CH═CHO(-)), imine (PCy2CH2CH═NR, R = Ph, (S)-CHMePh), and oxime (PCy2CH2CH═NOH) ligands. The phosphonium dimer, when deprotected with base, generates the phosphine aldehyde PCy2CH2CHO in situ, which, in the presence of [M(COD)Cl]2, M = Rh, Ir, and a PF6(-) salt, or [Ni(H2O)6][BF4]2, facilitates a condensation reaction with an amine or hydroxylamine to form phosphino-imine or phosphino-oxime metal complexes [M(COD)(P-N)][PF6] or [Ni(P-N)2][X]2, X = ClO4(-), BF4(-), respectively. In the absence of an amine, phosphino-enolate containing complexes are formed. A neutral Ni(II) complex Ni(PCy2CH═CHO)2 with trans-bis(phosphino-enolate) ligands which resemble ligands used on nickel for olefin oligomerization, as well as neutral Rh(I) and Ir(I) 1,5-cyclooctadiene complexes M(COD)(PCy2CH═CHO) are characterized. Both the rhodium and iridium complexes are active olefin hydrogenation catalysts. Reaction of the phosphino-aldehyde with Pt(COD)Cl2 results in the formation of trans-PtCl2(PCy2CH2CHO)2 with pendant aldehyde groups, and under certain conditions, they undergo an intraligand aldol condensation to form a disphosphine ligand.
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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) | 0.005 | 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".