Reactivity of Terminal, Electrophilic Phosphinidene Complexes of Molybdenum and Tungsten. Nucleophilic Addition at Phosphorus and P−P Bond Forming Reactions with Phosphines and Diphosphines
Bibliographic record
Abstract
Reaction of the terminal electrophilic phosphinidene complexes [Cp*M(CO) 3 {PN( i -Pr) 2 }][AlCl 4 ] ( 3, M = Mo; 4, M = W) with PEt 3 results in replacement of a metal carbonyl by the phosphine. The reactions occur via initial nucleophilic attack by the phosphine at the phosphinidene phosphorus, followed by carbonyl loss and migration of the phosphine to the metal. Reactions of 3 and 4 with bis(dimethylphosphino)methane (dmpm) lead to [Cp*M(CO) 2 {P(N( i -Pr) 2 )P(Me 2 )CH 2 P(Me 2 )-κ 2 P 1, P 4 }][AlCl 4 ] ( 9, M = Mo; 10, M = W), in which one end of the diphosphine coordinates to phosphorus and the other end coordinates to the metal. The reactions proceed by initial nucleophilic attack by one end of the diphosphine at phosphorus, followed by carbonyl loss and coordination of the other end of the ligand to the metal. Compound 3 (M = Mo) reacts with bis(dimethylphosphino)ethane (dmpe) to give the analogous product [Cp*Mo(CO) 2 {P(N( i -Pr) 2 )P(Me 2 )CH 2 CH 2 P(Me 2 )-κ 2 P 1, P 5 }][AlCl 4 ] ( 12 ), in which the two ends of the dmpe ligand coordinate to phosphorus and molybdenum, respectively. Reaction of compound 4 (M = W) with dmpe leads to two products, [Cp*W(CO) 2 {P(N( i -Pr) 2 )P(Me 2 )CH 2 CH 2 P(Me 2 )-κ 2 P 1, P 5 }][AlCl 4 ] ( 13 ) and [{Cp*W(CO) 2 (PN( i -Pr) 2 )} 2 (μ-dmpe)][AlCl 4 ] 2 ( 14 ). Compound 13 is analogous to 12 . In compound 14, the two ends of the diphosphine ligand displace carbonyl ligands from two molecules of 4, resulting in a novel bis-phosphinidene structure in which the diphosphine ligand bridges two metal centers, each of which retains a terminal phosphinidene ligand. Loss of an additional carbonyl ligand from 12, followed by migration of one end of the phosphine from phosphorus to the metal, results in re-formation of a terminal phosphinidene ligand, leading to [Cp*Mo(CO)(PN( i -Pr) 2 )(dmpe-κ 2 P )][AlCl 4 ] ( 17 ). The structural characterization of the phosphine adducts and carbonyl substitution products of the terminal phosphinidene complexes 3 and 4 has provided valuable insights into metal−phosphinidene bonding in these compounds.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".