In-depth NMR and IR study of the proton transfer equilibrium between [{(MeC(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>}Ru(CO)H<sub>2</sub>] and hexafluoroisopropanol
Bibliographic record
Abstract
The (carbonyl)dihydride complex [(triphos)Ru(CO)H 2 ] (2) has been synthesized by reaction of the ruthenate [(triphos)RuH 3 ]K (triphos = MeC(CH 2 PPh 2 ) 3 ) with ethanol saturated with CO. A single crystal X-ray analysis and IR and NMR experiments have shown that 2 adopts in both the solid state and solution an octahedral coordination geometry with a facial triphos ligand, two cis terminal hydrides, and a terminal carbonyl. The reaction of hexafluoro-2-propanol (HFIP) with 2 has been studied in CH 2 Cl 2 solution by IR and NMR spectroscopy. The proton donor interacts with a terminal hydride of 2 forming a rather strong hydrogen bond. The resulting H-bonded adduct [{(triphos)Ru(CO)(H)H}···{HOCH(CF 3 ) 2 }] (2a) has fully been characterized by in situ NMR and IR techniques. Compound 2a is in equilibrium with the nonclassical η 2 -H 2 complex [(triphos)Ru(CO)H(H 2 )] + (2b), which can independently be prepared by protonation of 2 with a strong protic acid at low temperature. Unequivocal characterization of the dihydrogen complex (2b) has been achieved by a multifaceted spectroscopic investigation (T obs 1min = 0.005 s (200 MHz), J H,D [Formula: see text] 30 Hz, DQCC = 78.3 kHz). A combined IR and NMR study of the proton transfer reaction involving 2 and HFIP in CH 2 Cl 2 to give, first, the H-bonded adduct (2a) and, then, the dihydrogen complex (2b) has demonstrated that all these species are in equilibrium in the temperature range from 190 to 260 K. The thermodynamic parameters for the formation of 2a have independently been determined by NMR and IR methods, while those for the formation of 2b have been obtained by IR spectroscopy. An energetic profile for the reaction sequence 2 [Formula: see text] 2a [Formula: see text] 2b is proposed and discussed.Key words: hydrides, hydrogen bonding, ruthenium, IR spectroscopy, NMR spectroscopy.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 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 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".