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 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 | 0.005 | 0.004 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.004 | 0.001 |
| Bibliometrics | 0.001 | 0.003 |
| Science and technology studies | 0.002 | 0.003 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.002 | 0.003 |
| Insufficient payload (model declined to judge) | 0.000 | 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; both teacher heads agree on what is shown here.
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".