Electron rich bidentate phosphinimine-imine ligands: Synthesis and reactivity of late transition metal complexes
Bibliographic record
Abstract
Electron rich phosphinimine-imine proligands Ph(3)PN(C(6)H(4))C(Ph)(NAr) (L(Ar)) (Ar = 4-(OEt)C(6)H(4) (OEt), 3,5-Me(2)C(6)H(3)(Xyl)) were synthesized in three steps from 2-aminobenzophenone. These compounds, along with previously reported L(Mes) and L(Tol) (Mes = 2,4,6-Me(3)C(6)H(2), Tol = 4-MeC(6)H(4)) were used to synthesize a series of tetracarbonyltungsten(0) complexes: L(Mes)W(CO)(4) (1), L(Tol)W(CO)(4) (2), L(OEt)W(CO)(4) (3), and L(Xyl)W(CO)(4) (4). The ligands were evaluated by analysis of the carbonyl stretching frequencies of the tungsten complexes and were shown to be better sigma-donors and poorer pi-acceptors compared to similar ligands in the literature. The coordination chemistry of the proligands was expanded to other late transition metals and L(Mes)CoCl(2) (5), L(Tol)CoCl(2) (6), L(Mes)NiBr(2) (7), L(Tol)NiBr(2) (8), L(Mes)ZnCl(2) (9), and L(Tol)ZnCl(2) (10) were synthesized by the direct reaction of L(Mes) and L(Tol) with the respective metal dihalide precursors. The complexes were fully characterized and the molecular structures of complexes 3, 6, 7, and 10 were reported. The synthesis of zinc complexes 9 and 10 was dependent on the steric bulk of the ligand. Complex 10 proved to be resistant to derivatization via a number of routes.
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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".