Theoretical and DFT Study of Atypical Pentanuclear [( <sup> <i>i</i> </sup> Pr <sub>3</sub> P)Ni] <sub>5</sub> H <sub> <i>n</i> </sub> ( <i>n</i> = 4, 6, 8) Clusters: What are the Rules?
Bibliographic record
Abstract
The structure, bonding, and properties of a series of atypical pentanuclear nickel hydride clusters supported by electron-rich i Pr 3 P of the type [( i Pr 3 P)Ni] 5 H n ( n = 4, 6, 8; H 4, H 6, H 8 ) and their anionic models where i Pr 3 P are substituted by H – ( H 4 ′, H 6 ′, H 8 ′ ) were investigated by density functional theory (DFT) calculations. All clusters were calculated to adopt a similar square pyramidal core geometry. Calculations indicate singlet ground states with small singlet–triplet gaps for H 4 and H 6, similar to previously reported experimental values. Molecular orbital theory description clusters were investigated using the simplified model complexes [HNi] 5 H n 5– ( n = 4, 6, 8; H 4 ′, H 6 ′, H 8 ′ ). The results show that there are three skeletal electron pairs (SEPs) in H 4 ′ . The addition of two molecules of H 2 to form H 6 ′ and H 8 ′ results in the partial or full occupation of two degenerate MOs ( e* set) that give two SEPs and one SEP, respectively. Indeed, the occupation of these low-lying weakly antibonding orbitals governs the multielectron chemistry available for these clusters and plays a role in their unique reactivity.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.002 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.002 |
| Research integrity | 0.001 | 0.002 |
| 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; both teacher heads agree on what is shown here.
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".