Activation of Imines by Platinum(II) To Give Aminoalkyl Complexes: Scope and Limitations of the Reaction
Bibliographic record
Abstract
Reaction of an excess of the ligand 1,2-C 2 H 4 (N CH-2-C 5 H 4 N) 2 ( 1 ), 1,2-C 2 H 4 (N CH-2-C 9 H 6 N) 2 ( 2 ), or 1,3-C 3 H 6 (N CH-2-C 5 H 4 N) 2 ( 3 ) with [Pt 2 Me 4 (μ-SMe 2 ) 2 ] gives the following platinum(II) complexes that contain a free imine functional group: [PtMe 2 {C 2 H 4 ( N CH-2-C 5 H 4 N )(N CH-2-C 5 H 4 N)}] ( 4 ), [PtMe 2 {C 2 H 4 ( N CH-2-C 9 H 6 N )(N CH-2-C 9 H 6 N)} ( 5 ), or [PtMe 2 {C 3 H 6 ( N CH-2-C 5 H 4 N )(N CH-2-C 5 H 4 N)}] ( 6 ) (C 5 H 4 N = pyridyl, C 9 H 6 N = quinolyl). The reaction of complexes 4 − 6 with excess CF 3 CO 2 H or HCl gave aminoalkylplatinum(IV) products, and it is suggested that the reactions occur by protonation of the free imine nitrogen atom followed by oxidative addition of the transient iminium group so formed. The products were formed as a mixture of isomers whose structures were deduced from their spectroscopic properties and, for the complexes [PtMe 2 {C 2 H 4 ( N CH-2-C 5 H 4 N )(NH 2 C H-2-C 5 H 4 NH)}(O 2 CCF 3 )][O 2 CCF 3 ] 2 ( 7a ) [PtMe 2 {C 2 H 4 ( N CH-2-C 5 H 4 N )(NH 2 C H-2-C 5 H 4 NH)}Cl][Cl] 2 ( 8a ), and [PtMe 2 {C 3 H 6 ( N CH-2- C 5 H 4 N )(NH 2 - C H-2-C 5 H 4 N)Cl][Cl] ( 14a ), by X-ray structure determinations. The reaction of 5 with an equimolar amount of CF 3 CO 2 H gave [PtMe 2 {C 2 H 4 ( N CH-2-C 9 H 6 N )(NH C H-2-C 9 H 6 N )}][CF 3 CO 2 ] ( 9 ), which was shown by X-ray structure determination to contain a four-membered azametallacyclobutane ring. Attempts to effect the intermolecular protonation/metalation of imines by platinum(II) were unsuccessful, since reactions of [PtMe 2 (bu 2 bpy)] (bu 2 bpy = 4,4 ‘ -di- tert -butylbipyridine) with N -benzylidenemethylamine or N -benzylideneaniline and CF 3 CO 2 H led only to protonolysis of the methyl−platinum bonds.
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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 | 0.001 |
| 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) | 0.007 | 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".