Properties of the [M(dppm)<sub>2</sub>M′]<sup>2+</sup> Building Blocks (M, M′ = Pd or Pt): Site Selectivity, Emission Features, and Frontier Orbital Analysis
Bibliographic record
Abstract
The homodinuclear [ClM(mu-dppm)(2)MCl] complexes 1 (M = Pd) and 2 (M = Pt) react with RNC ligands (R = Ph, xylyl, p-tolyl, p-C(6)H(4)iPr) to provide the A-frame [ClPd(mu-dppm)(2)(mu-C=N-R)PdCl] (R = Ph (5a), xylyl (5b)), [ClPt(mu-dppm)(2)(mu-C=N-R)PtCl] (R = p-tolyl (4a); p-C(6)H(4)iPr (4b)), and the d(9)-d(9) M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (R = xylyl (3a); p-C(6)H(4)iPr (3b)) complexes. The heterodinuclear [XPd(mu-dppm)(2)PtX] complexes 6a (X = Cl) and 6b (X = I) react with RNC (R = o-anisyl) to form the A-frame [XPd(mu-dppm)(2)(mu-C=N-R)PtX] (X = Cl (9); I (10a)) and M(2)-bonded [ClPt(mu-dppm)(2)Pt(CN-R)]Cl (10b) complexes. The dangling ligand-containing complex [ClPd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4)) (7) reacts with xylyl-NC stoichiometrically to produce the dicationic salt [(xylyl-NC)Pd(mu-dppm)(2)Pt(eta(1)-dppm=O)](BF(4))(2) (8). Parameters ruling the coordination site terminal versus bridging are discussed. The precursor 10a reacts with RNC (R = o-anisyl, tBu) to form the heterobimetallic bis(isonitrile) [IPd(mu-dppm)(2)(mu-C=N-o-anisyl)Pt(CN-R)]I complexes 11b and 12, respectively, demonstrating the site selectivity of the second CNR ligand coordination, Pd versus Pt. The X-ray structures of 11b and 12 were obtained. Complex 12 is the first example of an A-frame system of the Ni-triad bearing two different isocyanide ligands. Several d(9)-d(9) terminal and d(8)-d(8) A-frame homo- and heterodinuclear complexes in 2-MeTHF at 77 K were studied by UV-vis and luminescence spectroscopy. Assignments for the lowest energy absorption and emission bands are made on the basis of density functional theory and time-dependent density functional theory computations.
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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".