New Bonding Modes for Boraamidinate Ligands in Heavy Group 15 Complexes: Fluxional Behavior of the 1:2 Complexes, LiM[PhB(N<i><sup>t</sup></i>Bu)<sub>2</sub>]<sub>2</sub> (M = As, Sb, Bi)
Bibliographic record
Abstract
The reactions of MCl3 with Li2[PhB(NtBu)2] in 1:1, 1:1.5, and 1:2 molar ratios in diethyl ether produced the monoboraamidinates ClM[PhB(NtBu)2] (1a, M = As; 1b, M = Sb; 1c, M = Bi), the novel 2:3 boraamidinate complexes [PhB(NtBu)2]M-micro-N(tBu)B(Ph)N(tBu)M[PhB(NtBu)2] (2b, M = Sb; 2c, M = Bi), and the bisboraamidinates LiM[PhB(NtBu)2]2 (3a, 3a.OEt2, M = As; 3b, M = Sb; 3c.OEt2, M = Bi), respectively. The 2:3 complexes 2b and 2c were also observed in the reactions carried out in a 1:2 molar ratio at room temperature. All complexes have been characterized by multinuclear NMR spectroscopy (1H, 7Li, 11B, and 13C) and by single-crystal X-ray structural determinations. The molecular units of the mono-boraamidinates 1a-c are isostructural, but their crystal packing is distinct as a result of stronger intermolecular close contacts going from 1a to 1c. In the novel 2:3 bam complexes 2b and 2c, each metal center is N,N'-chelated by a bam ligand and these two [M(bam)]+ units are bridged by the third [bam]2- ligand. The structures of the unsolvated bis-boraaminidate complexes 3a and 3b consist of [Li(bam)]- and [M(bam)]+ monomeric units linked by Li-N and M-N bonds to give a tricyclic structure. Solvation of the Li+ ion by diethyl ether results in a bicyclic structure composed of four-membered BN2As and six-membered BN3AsLi rings in 3a.OEt2. In contrast, the analogous bismuth complex 3c.OEt2 exhibits a tetracyclic structure. Variable-temperature NMR studies reveal that the nature of the fluxional behavior of 3a-c in solution is dependent on the group 15 center.
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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) | 0.003 | 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".