Sterically Hindered and Robust Pnictogen Ligands Derived from Carboranes: Synthesis and X-ray Structure Determination of Tris(1‘-methyl(1,2-dicarba-<i>c</i><i>loso</i>-dodecaboran-1-yl))phosphine, Tris(1‘-methyl(1,2-dicarba-<i>c</i><i>loso</i>-dodecaboran-1-yl))arsine and Chloro(Tris(1‘-methyl(1,2-dicarba-<i>c</i><i>loso</i>-dodecaboran-1-yl))phosphine)gold(I)
Why this work is in the frame
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Bibliographic record
Abstract
Sterically hindered phosphine and arsine ligands derived from ortho-carborane were synthesized and characterized by X-ray crystallography. Tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine, 2 (crystal data, hexagonal, space group P6(3), a = b = 12.251(3) A, c = 11.514(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1496.6(7) A(3), Z = 2, R(1) = 0.0568) and tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))arsine, 3 (crystal data, hexagonal, space group P6(3), a = b = 12.330(3) A, c = 11.474(4) A, alpha = beta = 90 degrees, gamma = 120 degrees, V = 1510.7(7) A(3), Z = 2, R(1) = 0.0930) were prepared in 82% and 68% yield, respectively. The phosphine ligand is resistant to air-oxidation but was converted to corresponding oxide when heated with hydrogen peroxide. The tertiary carboranyl phosphine reacted with (Tht)AuCl to yield chloro(tris(1'-methyl(1,2-dicarba-closo-dodecaboran-1-yl))phosphine)gold(I), 4 (crystal data, monoclinic, space group P2(1)/c, a = 19.101(4) A, b = 12.167(2) A, c = 13.846(3) A, alpha = gamma = 90 degrees, beta = 91.13(3) degrees, V = 3217.2(11) A(3), Z = 4, R(1) = 0.0396) in 82% yield. From the X-ray structure of the gold complex, the cone angle of the phosphine was determined to be 213(2) degrees, which is among the largest values reported to date.
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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 | 0.002 | 0.004 |
| Meta-epidemiology (narrow) | 0.005 | 0.005 |
| Meta-epidemiology (broad) | 0.008 | 0.001 |
| Bibliometrics | 0.001 | 0.004 |
| Science and technology studies | 0.001 | 0.004 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.003 | 0.002 |
| Research integrity | 0.005 | 0.005 |
| Insufficient payload (model declined to judge) | 0.001 | 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 it