Preparation, Structure, and Metallophilic Interactions of Dinuclear Silver(I) and Copper(I) Complexes of Selenium Diimides
Bibliographic record
Abstract
The complexes [M(2){mu-N,N'-Se(NR)(2)}(2)](CF(3)SO(3))(2) (1, M = Ag, R = (t)Bu; 2, M = Ag, R = Ad; 3, M = Cu, R = (t)Bu; 4, M = Cu, R = Ad; Ad = 1-adamantyl) were prepared in good yields from the reaction of the corresponding selenium diimide with silver or copper triflate in toluene and were characterized in solution using multinuclear NMR spectroscopy. Recrystallization of 1-4 from a variety of solvents produced 1.2CH(2)Cl(2), 2(AdNH(3))(CF(3)SO(3)) (a few crystals), 3.2thf, and 4.1/2C(7)H(8), which were characterized by X-ray crystallography. All of these salts contain a metallacyclic [M(2){mu-N,N'-Se(NR)(2)}(2)](2+) [M = Ag, Cu; R = (t)Bu, Ad] cation, the frameworks of which exhibit M...M close contacts of 2.7384(9), 2.751(2), 2.556(2)-2.569(2), and 2.531(1) A, respectively. The M...M interaction was further explored by PBE/def-TZVP calculations of the dications [M(2){mu-N,N'-Se(NR)(2)}(2)](2+) (M = Ag, Cu; R = H, Me, (t)Bu, Ad). The geometry optimizations yielded metric parameters that were in good agreement with experimental values, where available. For both metals, it was observed that the M...M distance became shorter, as the organic substituent on nitrogen became bulkier. At the same time, the metallacyclic framework deviated more significantly from planarity. A survey of related dinuclear silver(I) and copper(I) complexes showed that, while there is some correlation between the bite size and the M...M distance, the latter is more dependent on the deviation from planarity of the D(2)M...MD(2) fragment. Atoms in molecules calculations clearly showed the presence of a bond critical point between the two silver or copper centers, as well as two ring critical points. Our computational results are consistent with other recent molecular orbital studies at different levels of theory and indicate the existence of d(10)-d(10) closed-shell metallophilic interactions in 1-4.
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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 | 0.000 |
| 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) | 0.007 | 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".