Synthesis and Reactivity of New κ<sup>2</sup>-[<i>P</i>,<i>N</i>]Pt(II) Complexes of Diisopropylphosphino-Substituted 2-Dimethylaminoindene
Bibliographic record
Abstract
Treatment of 1-P i Pr 2 -2-NMe 2 -indene ( 1a [H]) with either cis / trans -(SMe 2 ) 2 PtCl 2 or PtCl 2 provided (κ 2 - P,N -2-NMe 2 -3-P i Pr 2 -indene)PtCl 2 ( 2 ) in 84% and 55% yield, respectively, while the reaction of 1a [H] with (η 4 -COD)PtClMe afforded (κ 2 - P,N -2-NMe 2 -3-P i Pr 2 -indene)PtClMe ( 3 ) in 91% yield. Whereas in the formation of 2 and 3 the ligand precursor 1a [H] undergoes a rearrangement to give a coordinated 2-NMe 2 -3-P i Pr 2 -indene ( 1b [H]) ligand, 1a [H] reacted cleanly with 0.5 equiv of [(μ-SMe 2 )PtMe 2 ] 2 to give (κ 2 - P, N - 1a [H])PtMe 2 ( 4a ) in 97% yield. The isomerization of 4a to (κ 2 - P, N - 1b [H])PtMe 2 ( 4b ) in a THF/ i PrOH mixture is rapid and allowed for the isolation of 4b in 99% yield. Heating of 4a in CH 2 Cl 2 resulted in the quantitative formation of 3, while the thermolysis of 4a in toluene in the presence of SMe 2 afforded 5, the apparent product of intramolecular C−H activation of an NMe group. The reactivity of 4a with a variety of other two-electron donors, as well as E−H-containing substrates (E = main group fragment), is reported. Although NMR spectroscopic evidence indicated the formation of an intermediate of the type (κ 2 - P, N - 1 [H])Pt(SnPh 3 )(Me), as well as Ph 6 Sn 2, in the reaction of 4a with 10 equiv of Ph 3 SnH, negligible conversion of Ph 3 SnH to Ph 6 Sn 2 was obtained when employing 1 mol % 4a as a catalyst. Single-crystal X-ray diffraction data for 2 and 5 are reported.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 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".