Organometallics versus P<sub>4</sub> Complexes of Group 11 Cations: Periodic Trends and Relativistic Effects in the Involvement of (<i>n</i>−1)d, <i>n</i>s, and <i>n</i>p Orbitals in Metal−Ligand Interactions
Bibliographic record
Abstract
The nature of the bonding in ethylene and η 2 -P 4 complexes, M(C 2 H 4 ) 2 + and M(η 2 -P 4 ) 2 +, of group 11 metal cations (M = Cu, Ag, Au) has been explored by density functional calculations. On the basis of the evaluation of symmetry orbitals, the contributions from the interactions of ligand orbitals with metal n s, n p, and ( n −1)d orbitals have been investigated. The analysis shows that the metal−ligand bonds in the organometallics and phosphorus complexes fit to a unified scheme, whereas traditional concepts such as the isolobality principle would hardly predict such a bonding analogy between C 2 H 4 and P 4 complexes. Bond energies increasing in the order Ag < Cu < Au have been predicted. The stronger metal−ligand bonds in the gold(I) compounds compared to those in the silver(I) compounds can be elucidated by the relativistic stabilization of the orbital interactions, particularly of those involving 6s and 5d orbitals. The stronger metal−ligand bonds in Cu(η 2 -P 4 ) 2 + compared to those in the experimentally known Ag(η 2 -P 4 ) 2 + can be attributed partly to the strong back-donation from metal 3d orbitals to vacant ligand orbitals. This result stands in sharp contrast to the common belief that first-row transition metals form weaker bonds to ligands than do their second-row analogues because of a comparably small overlap between ligand orbitals and metal 3d orbitals.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".