Bis(carbonyl)platinum(II) Derivatives: Molecular Structure of<i>cis</i>-Pt(CO)<sub>2</sub>(SO<sub>3</sub>F)<sub>2</sub>, Complete Vibrational Analysis of<i>cis</i>-Pt(CO)<sub>2</sub>Cl<sub>2</sub>, and Attempted Synthesis of<i>cis</i>-Pt(CO)<sub>2</sub>F<sub>2</sub>
Bibliographic record
Abstract
As part of a comprehensive study of square planar palladium(II) and platinum(II) carbonyl derivatives, the molecular structure of cis -Pt(CO) 2 (SO 3 F) 2, the complete vibrational spectra of cis -Pt(CO) 2 Cl 2, and the attempted synthesis of cis -Pt(CO) 2 F 2 are reported. cis -Pt(CO) 2 (SO 3 F) 2 is isostructural with cis -Pd(CO) 2 (SO 3 F) 2 and crystallizes in the monoclinic space group P 2 1 / n (no. 14). Crystal data: a = 7.419(1) Å; b = 14.751(2) Å; c = 8.634(1) Å; β = 89.95(1)°; V = 944.9(2) Å 3; Z = 4; T = 300 K; R [ F o > 4σ( F o )] = 0.0447 and wR2 = 0.1097. The internal bond parameters of the cis -Pt(CO) 2 (SO 3 F) 2 are compared to those of cis -Pd(CO) 2 (SO 3 F) 2, cis -Pt(CO) 2 Cl 2, and [M(CO) 4 ] 2+, M = Pd, Pt. Solid cis -Pt(CO) 2 Cl 2 is studied by IR and Raman spectroscopy, and the data are compared to those of the matrix-isolated complex by IR spectroscopy. Vibrational assignments are supported by DFT calculations, which provide, in addition to vibrational wavenumbers, estimates of IR and Raman band intensities. The positions of 12 of the expected 15 fundamentals of cis -Pt(CO) 2 Cl 2 are obtained experimentally. Attempts to synthesize cis -Pt(CO) 2 F 2, using, in addition to cis -Pt(CO) 2 X 2, X = Cl or SO 3 F, [Pt(CO) 4 ][Sb 2 F 11 ] 2 or PtF 6 as starting material and toluene or anhydrous hydrogen fluoride as the reaction medium, are unsuccessful. There are however two interesting results: The reductive carbonylation of PtF 6 in HF produces with [Pt(CO) 4 ][PtF 6 ] the first carbonyl fluoride of platinum, and the reaction of [Pt(CO) 4 ][Sb 2 F 11 ] 2 and CsF in HF results in the formation of the previously reported anionic cluster complex Cs 2 [Pt 3 (CO) 6 ] n ≈ 10 . The inclusion of [M(CO) 4 ] 2+, M = Pd, Pt, provides new insights into the nature of the Pd(II)−CO and Pt(II)−CO bonds.
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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 | 0.000 | 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".