Reactivity of SiMe<sub>3</sub>- and SnR<sub>3</sub>-Functionalized Bis(7-azaindol-1-yl)methane with [PtR<sub>2</sub>(μ-SMe<sub>2</sub>)]<sub><i>n</i></sub>(R = Me, Ph) and the Resulting Pt(II) and Pt(IV) Complexes
Bibliographic record
Abstract
Three new bis(7-azaindol-1-yl)methane (BAM) derivative ligands Me 3 Si-BAM ( 1a ), Me 3 Sn-BAM ( 1b ), and Ph 3 Sn-BAM ( 1c ) have been synthesized, and their reactivities with [PtR 2 (μ-SMe 2 )] n (R = Me, Ph) have been examined. Two Pt(II) complexes Pt(Me 3 Si-BAM)R 2 (R = Me, 2; Ph, 3 ) were obtained from the reactions of 1a . The reactions of 1b with [PtR 2 (μ-SMe 2 )] n (R = Me, Ph) produced unexpected novel N, C, N -BAM Pt(IV) complexes Pt( N, C, N- BAM)(SnMe 3 )R 2 (R = Me, 4; Ph, 6 ) likely via oxidative cleavage of the C BAM −Sn bond in 1b . 1c reacted with [PtPh 2 ( μ- SMe 2 )] n ( n = 2, 3) yielding the anticipated Pt(II) complex Pt(Ph 3 Sn-BAM)Ph 2 ( 7 ), whereas its reaction with [PtMe 2 (μ-SMe 2 )] 2 resulted in unusual Pt II - Me and Sn IV - Ph metathesis, yielding also 7 as one of the products. Mechanistic investigation was carried out to understand this phenomenon. The reactivities of 2 with MeI, MeOTf, and I 2 were examined. Its reaction with I 2 gave rise to Pt(Me 3 Si-BAM)I 2 ( 9 ) along with CH 3 I, indicating the possibility of functionalizing Pt II - Me via iodinolysis. The reaction of Pt( N, C, N- BAM)(SnMe 3 )Me 2 ( 4 ) with I 2 produced a number of unusual N, C, N -BAM Pt(IV) complexes including Pt( N, C, N -BAM)Me(I)(SnI 2 Me) ( 13 ) and Pt( N,C,N -BAM)Me(I)(I 3 ) ( 14 ) due to the electrophilic cleavage of the Sn-Me, Pt-Me and/or Pt−Sn bond(s) by I 2 . For comparison, we also investigated the reaction of Pt( N, C, N -BAM)Me 3 ( M1 ) with I 2 which was found to exhibit a high regioselectivity for the axial Pt-Me group, resulting in Pt( N, C, N -BAM)Me 2 (I 3 ) ( 15 ) with the two Pt- Me being cis to each other. The reactions of 4 and M1 with I 2 are rare examples of Pt IV −CH 3 bond cleavage by the elimination of CH 3 I. The structures of 1a and complexes 2, 7, 9, and 13 − 15 were determined by X-ray diffraction analyses.
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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) | 0.002 | 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".