Synthesis and Structure of Group 4 Iminophosphonamide Complexes
Bibliographic record
Abstract
The syntheses of a variety of iminophosphonamide (PN 2 ) ligands ( 2a − f ), the corresponding hydrochloride salts ( 1a − c ), and a number of bis(PN 2 ) dichloride complexes of group 4 ( 3a − e ) and their corresponding dialkyls ( 5a − e ) are described. A novel monosubstituted PN 2 “ate” complex 4 was prepared from ligand 2f and Zr(NMe 2 ) 4 on treatment with excess Me 2 NH·HCl. Piano-stool PN 2 zirconium dichloride complexes 6a − h were accessible on treatment of CpZr(NMe 2 ) 3 (Cp = C 5 H 5, Cp*) with PN 2 ligands 2a − e, followed by metathesis with excess Me 3 SiCl or Me 2 NH·HCl ( 6a − g ) or at low T with ethereal HCl ( 6h ). Dialkyl derivatives 8a − h could be prepared from 6a − h or directly from ligands 2 and CpMMe 3 (Cp = C 5 H 5, Cp*; M = Ti or Zr). The intermediate Cp(PN 2 )Zr(NMe 2 ) 2, precursor to 6h, rearranged to the novel terminal difluoride complexes 7a, b at room temperature. A variety of complexes 3 and 6 or their corresponding alkyl derivatives have been characterized by X-ray crystallography. In addition, the novel “ate” complex 4 and difluoride complexes 7a, b have been structurally characterized in this manner. The structures of 7a, b in the solid state reveal strong, intramolecular coordination of the NMe 2 group to the metal center, resulting in eight-coordinate complexes. One of these complexes is fluxional in solution, suggesting rapid exchange of bound versus free NMe 2 groups coupled with the formation of coordination stereoisomers.
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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) | 0.001 | 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) | 0.062 | 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".