Solid-state 13C and 59Co NMR spectroscopy of 13C-methylcobalt(iii) complexes with amine ligands
Bibliographic record
Abstract
Five octahedral Co(iii) cations, [trans-Co(en)(2)(X)((13)CH(3))](n+) where en = ethylenediamine, X = CN(-), N(3)(-), NH(3), NO(2)(-) or H(2)O and n = 1 or 2, as well as [Co(NH(3))(5)(13)CH(3)](2+), have been investigated by solid-state (13)C and (59)Co NMR spectroscopy. We show that the determination of the (59)Co nuclear quadrupolar parameters both directly via(59)Co NMR and indirectly via(13)C NMR provide complementary information that is unavailable if one investigates only one nucleus. Specifically, (1)J((59)Co,(13)C) and the orientation of the largest component of the EFG were determined via(13)C NMR spectroscopy, which also established the negative sign of C(Q)((59)Co). Cobalt-59 NMR spectroscopy was used to characterize the cobalt magnetic shielding tensor, to verify the magnitudes of C(Q)((59)Co) and to establish the value of eta(Q), which is difficult to determine indirectly. The measurements show that the EFG tensors are either axially symmetric or close to being so, but there is a wide range of C(Q) values, from -40 MHz for the complex with X = H(2)O to -105 MHz with X = CN(-). The Co chemical shift tensors are approximately axially symmetric with the spans, delta(11)-delta(33), ranging from 3700 to 5600 ppm for X = H(2)O and CN(-), respectively. The latter measurements also established the relative orientations of the Co EFG and chemical shift tensors. Density functional theory calculations of the (59)Co EFG and magnetic shielding tensors as well as of (1)J((59)Co,(13)C) for the NO(2)(-) and N(3)(-) complexes were undertaken. These calculations confirm the experimental observation that the sign of C(Q) is negative and that the largest component of the EFG is along the Co-methyl-carbon bond.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".