Blue Copper Protein Model Compounds Containing Stable Cu–S Bonds: Structure, Properties, and Function
Bibliographic record
Abstract
This chapter describes the synthesis and characterization of model complexes for blue copper protein. The protein’s primary function is ubiquitous electron transfer. Its name is due to the characteristic color that among other properties of its active site was a synthetic target for coordination chemists. Molecular complexes were designed with “the blue copper” absorption band, narrow A|| hyperfine coupling constant from electron paramagnetic resonance spectroscopy, high redox potentials, and characteristic Cu–S bond features from resonance Raman spectroscopy. These together indicate a trigonal pyramidal copper(ii) coordination. In contrast, the green colored, normal copper(ii) complexes have a tetragonal coordination geometry with the Cu–S bond that readily undergoes homolytic cleavage. We used a sterically hindered N3 tripodal ligand, hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (L1−) to protect the reactive Cu–S bond. Our synthetic efforts allowed for the structural characterization of four-coordinate thiolato copper(ii) complexes [CuII(SC6F5)(L1)] and [CuII(SCPh3)(L1)] featuring distorted trigonal pyramidal copper(ii) geometry. Both complexes reproduce well the spectroscopic features of blue copper proteins. Furthermore, we also characterized a five-coordinate thiolato copper(ii) complex [CuII(SMeIm)(L1)], whose structure is described as tetragonal pyramidal due to the S,N-chelate forming thiolate ligand. The experimental results were supplemented with electronic structure calculation to determine their metal–ligand chemical bonding profile.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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 | 0.001 |
| 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 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".