Homoleptic, σ-Bonded Octahedral [M(CO)<sub>6</sub>]<sup>2+</sup> Cations of Iron(II), Ruthenium(II), and Osmium(II): Part 1: Syntheses, Thermochemical and Vibrational Characterizations, and Molecular Structures as [Sb<sub>2</sub>F<sub>11</sub>]<sup>-</sup> and [SbF<sub>6</sub>]<sup>-</sup> Salts. A Comprehensive, Comparative Study
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Bibliographic record
Abstract
Homoleptic octahedral, superelectrophilic sigma-bonded metal carbonyl cations of the type [M(CO)(6)](2+) (M = Ru, Os) are generated in the Bronsted-Lewis conjugate superacid HF/SbF(5) by reductive carbonylation of M(SO(3)F)(3) (M = Ru, Os) or OsF(6). Thermally stable salts form with either [Sb(2)F(11)](-) or [SbF(6)](-) as anion, just as for the previously reported [Fe(CO)(6)](2+) cation. The latter salts are generated by oxidative (XeF(2)) carbonylation of Fe(CO)(5) in HF/SbF(5). A rationale for the two diverging synthetic approaches is provided. The thermal stabilities of [M(CO)(6)][SbF(6)](2) salts, studied by DSC, range from 180 degrees C for M = Fe to 350 degrees C for M = Os before decarbonylation occurs. The two triads [M(CO)(6)][SbF(6)](2) and [M(CO)(6)][Sb(2)F(11)](2) (M = Fe, Ru, Os) are extensively characterized by single-crystal X-ray diffraction and vibrational and (13)C NMR spectroscopy, aided by computational studies of the cations. The three [M(CO)(6)][SbF(6)](2) salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereas the corresponding [Sb(2)F(11)](-) salts are monoclinic, crystallizing in space group P2(1)/n (No. 14). In both triads, the unit cell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF(6)](-) and [Sb(2)F(11)](-) and their vibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational properties of the [M(CO)(6)](2+) cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independent of M and nearly identical. Interionic C...F contacts are similarly weak in all six salts. Metal dependency is noted only in the (13)C NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-O stretching fundamentals (A(1g) and T(1u)). The findings reported here are unprecedented among metal carbonyl cations and their salts.
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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) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.002 | 0.002 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.002 |
| Research integrity | 0.002 | 0.002 |
| 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 it