Synthesis, Structure, and Reactivity of an Unusual Platinum Olefin Carbene Complex, [(η<sup>4</sup>-cod)Pt{C(Ph<sub>2</sub>PNSiMe<sub>3</sub>)<sub>2</sub>-κ<i>C</i>,κ<i>N</i>}]
Bibliographic record
Abstract
The organolithium dimer [Li 2 C(Ph 2 P NSiMe 3 ) 2 ] 2 ([Li 2 - 1 ] 2 ) reacts with 2 equiv of [PtCl 2 (cod)] (cod = 1,5-cyclooctadiene) in Et 2 O solution to give the novel Pt−carbene complex [(η 4 -cod)Pt{ C(Ph 2 P NSiMe 3 ) 2 -κ C,κ N }] ( 2 ), which is characterized by a relatively long Pt−C(carbene) bond and relatively short Pt−C(olefin) interactions indicative of an electron-rich Pt center. Under oxygen- and moisture-free conditions, 2 is remarkably inert; the cod ligand is not displaced by either monodentate or bidentate phosphines, phosphine sulfide, phosphite, or pyridine at room temperature, nor is the four-membered C,N-chelate ring opened by these reagents. However, 2 reacts with the electrophiles MeOTf (OTf = trifluoromethanesulfonate) and CO 2 . In the former case, the uncoordinated N atom of 2 is methylated to form [(η 4 -cod)Pt{ C(Ph 2 P NSiMe 3 )(Ph 2 P N(Me)SiMe 3 -κ C,κ N }][OTf] ( 3 ). In the latter, initial nucleophilic attack by the uncoordinated N atom on CO 2, followed by trimethylsilyl group migration from N to O, gives [(η 4 -cod)Pt{ C(Ph 2 P NSiMe 3 )(Ph 2 P NC(O)OSiMe 3 -κ C,κ N }] ( 4 ). Heating a benzene solution of 2 to 100 °C in a sealed tube for several hours, or to 60 °C for 10 min in the presence of H 2 O, yields the ortho-metalated complex [(η 4 -cod)Pt{CH(Ph(C 6 H 4 )P NSiMe 3 )(Ph 2 P NSiMe 3 )-κ C,κ C ‘ }] ( 5 ), which is characterized by Pt−C distances that are in the typical range for Pt−C(alkyl) and Pt−C(arene) interactions. The diastereoselectivity of the ortho metalation is consistent with an oxidative addition (nucleophilic) reaction mechanism for the ortho metalation. In contrast to 2, 5 displays typical cod substitution reactivity with chelating phosphines. The reaction between [Li 2 - 1 ] 2 and [PtCl 2 (cod)] in C 6 H 6 solution proceeds only very slowly and gives [Li][Pt{CH(Ph(C 6 H 4 )P NSiMe 3 )(Ph 2 P NSiMe 3 )-κ C,κ C ‘ }{CH(Ph 2 P NSiMe 3 ) 2 -κ C,κ N }] ( 7 ) in low yield.
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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 | 0.000 |
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".