Li/X Phosphinidenoid Pentacarbonylmetal Complexes: A Combined Experimental and Theoretical Study on Structures and Spectroscopic Properties
Bibliographic record
Abstract
The synthesis of P-F phosphane metal complexes [(CO)5M{RP(H)F}] 2a-c (R = CH(SiMe3)2; a: M = W; b: M = Mo; c: M = Cr) is described using AgBF4 for a Cl/F exchange in P-Cl precursor complexes [(CO)5M{RP(H)Cl}] 3a-c; thermal reaction of 2H-azaphosphirene metal complexes [(CO)5M{RP(C(Ph)═N}] 1a-c with [Et3NH]X led to complexes 3a-c, 4, and 5 (M = W; a-c: X = Cl; 4: X = Br; 5: X = I). Complexes 2a-c, 3a-c, 4, and 5 were deprotonated using lithium diisopropylamide in the presence of 12-crown-4 thus yielding Li/X phosphinidenoid metal complexes [Li(12-crown-4)(Et2O)n][(CO)5M(RPX)] 6a-c, 7a-c, 8, and 9 (6a-c: M = W, Mo, Cr; X = F; 7a-c: M = W, Mo, Cr; X = Cl; 8: M = W; X = Br; 9: M = W; X = I). This first comprehensive study on the synthesis of the title compounds reveals metal and halogen dependencies of NMR parameters as well as thermal stabilities of 6a, 7a, 8, and 9 in solution (F > Cl > Br > I). DOSY NMR experiments on the Li/F phosphinidenoid metal complexes (6a-c; M = W, Mo, Cr) rule out that the cation and anion fragments are part of a persistent molecular complex or tight ion pair (in solution). The X-ray structure of 6a reveals a salt-like structure of [Li(12-crown-4)Et2O][(CO)5W{P(CH(SiMe3)2)F}] with long P-F and P-W bond distances compared to 2a. Density functional theory (DFT) calculations provide additional insight into structures and energetics of cation-free halophosphanido chromium and tungsten complexes and four contact ion pairs of Li/X phosphinidenoid model complexes [Li(12-crown-4)][(CO)5M{P(R)X}] (A-D) that represent principal coordination modes. The significant increase of the compliance constant of the P-F bond in the anionic complex [(CO)5W{P(Me)F}] (10a) revealed that a formal lone pair at phosphorus weakens the P-F bond. This effect is further enhanced by coordination of lithium and/or the Li(12-crown-4) countercation (to 10a) as in type A-D complexes. DFT calculated phosphorus NMR chemical shifts allow for a consistent interpretation of NMR properties and provide a preliminary explanation for the "abnormal" NMR shift of P-Cl derivatives 7a-c. Furthermore, calculated compliance constants reveal the degree of P-F bond weakening in Li/F phosphinidenoid complexes, and it was found that a more negative phosphorus-fluorine coupling constant is associated with a larger relaxed force constant.
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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) | 0.019 | 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".