Tungsten coordination chemistry of 1,4-bisdiphenylphosphinobutadiyne — Synthesis of coordination macrocycles and factors controlling diyne cycloaddition
Bibliographic record
Abstract
The 1:1 reaction of [W(CO)4(2-picoline)2] (1) with Ph2PCtriple bondC-Ctriple bondCPPh2 (2) led to {[cis-W(CO)4]2(µ-Ph2PC4PPh2)2} (3), in which two bis(diphenylphosphino)butadiyne ligands bridge two tetracarbonyltungsten centres. Reaction of 1 with excess 2 led to [cis-W(CO)4(Ph2PC4PPh2-κ1-P)2] (4), in which two dangling bis-phosphines are coordinated to one metal centre, and reaction of 2 with two equivalents of 1 led to {[W(2-picoline)(CO)4]2(µ-Ph2PC4PPh2)} (5), in which one ligand bridges two tungsten centres. Combination of 4 and 5 led to the trimeric complex {[cis-W(CO)4]3(µ-Ph2PC4PPh2)3} (6), in which three tetracarbonyltungsten centres are bridged by three bisdiphenylphosphinobutadiyne ligands. The dimeric complex 3 showed no reactivity towards alkyne cycloaddition; however, the trimeric complex 6 undergoes cycloaddition at moderate temperatures to form {[W(CO)4]3[µ3-C12(Ph2P)6]} (8), which contains a cyclododecatrienetriyene ring. Comparison of structural data for the template complexes 3 and 6, as well that of previously described platinum template complexes, suggests that alkyne cycloaddition reactions are favoured by proximity of the alkynyl carbons α to phosphorus in adjacent ligands.Key words: coordination chemistry, diyne, cycloaddition, templated reaction, tungsten.
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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 | 0.000 | 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".