Symmetric Heteropolynuclear Ti(IV)/Cu(I) Complexes Exhibiting Stepwise Electrochemical Reductions to Ti(III) Species
Bibliographic record
Abstract
The heterotrinuclear complexes, [(CpTiCl(2)Cp-PPh(2))(2)Cu](+) (2) (as PF(6)(-) salt) and [CpTiCl(2)Cp-PPh(2)](2)CuCl (3), containing two electron-poor Ti(IV) fragments and one electron-rich Cu(I) center, and a tetrametallic species, [(CpTiCl(2)Cp-PPh(2))Cu(mu-Cl)](2) (4), were synthesized and characterized. The trinuclear nature of 2 and 3 was demonstrated by X-ray crystallography for which the three metallic centers are held together by two CpPPh(2) ligands. Weak Cl...Cu interactions are noted in 3, whereas two stronger Cl-Cu bridges are depicted in the cationic complex 2. The tetranuclear complex 4 contains two Cu atoms bridged together by two chloride ligands and connected to one Ti atom by one CpPPh(2) ligand and one mu-Cl ligand. Despite the short distances in the Ti-Cl-Cu bridges, notably in 2 and 4, the NMR spectra reveals evidence of fluxion in solution attributed to the lability of the mu-Cl ligands. Electrochemical experiments performed on 2 (rotating disk electrode and cyclic voltammograms) demonstrated the presences of two successive 1-electron reductions generating a first structurally unsymmetrical paramagnetic species [(CpTiCl(2)Cp-PPh(2))(2)Cu](0) (2'), confidently characterized by electron paramagnetic resonance (EPR) as a Ti(III)-Cu(I)-Ti(IV) system, and a second one, which is tentatively assigned to a symmetric neutral complex formulated as [CpTiClCp-PPh(2)](2)CuCl (5) with an EPR signature indistinguishable from that of 2' (i.e., Ti(III)-Cu(I)-Ti(III) system with a similar electronic environment). Density functional theory (DFT) computations examining the nature of the frontier orbitals and the geometry confirmed the presence and lack of symmetry in 2 and 2', respectively. The detection of chemical/electrochemical mechanisms in the electrochemical studies provides a clear explanation for the stepwise reduction behavior in these systems through chloride ligand transfer from Ti to Cu prior to the first reduction step. This transfer process is fully reversible upon re-oxidation. The electrochemical properties of complexes 3 and 4 are also reported.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 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".