Synthesis and properties of iron-group hydrido-cyano complexes trans-[MH(CN)(L)2], M = Fe, Ru or Os, L = diphosphine, and their hydrogen, trifluoroboron and triphenylboron isocyanide derivatives of the type trans-[MH(CNH)(L)2]O3SCF3, trans-[MH(CNBX3)(L)2], X = F or Ph, and trans-[M(H2)(CNBF3)(dppp)2]BF4 [dppp = Ph2P(CH2)3PPh2]
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Complexes trans-[MH(CN)L2] 1 {L = PPh2(CH2)nPPh2, n = 1 (dppm), 2 (dppe) or 3 (dppp), and PR2CH2CH2PR2, R = Et (depe) or para-tolyl (dtpe), M = Fe (for dppe, depe and dtpe only), Ru or Os} were prepared by displacing with cyanide the halide from trans-[MH(X)L2], X = Br or Cl, or dihydrogen from trans-[Ru(H2)H(dppe)2]BPh4. Systematic trends in the IR and 1H, 31P and 13C NMR and electrochemical properties are noted. The addition of one equivalent of HOTf (HO3SCF3) or [HPPh3]OTf to trans-[MH(CN)L2] 1 with n = 1, 2 or 3 usually produces the hydrogen isocyanide complexes trans-[MH(CNH)L2]OTf 2. The use of 13CN− or C15N− in compounds 1 provides evidence for the MCNH coordination mode over MNCH. Protonation at the M–H bond to give dihydrogen complexes trans-[M(H2)(CN)L2]+ occurs to a small degree for M = Ru, n = 1 or 3, in CH2Cl2 and completely for M = Os, L = depe. The use of HBF4· Et2O results in a variety of products including trans-[MH(CNH)L2]BF42*, trans-[MH(CNBF3)L2] and trans-[M(H2)(CNBF3)L2]+. The dihydrogen ligand in the last compound with M = Ru, L = dppp, is readily replaced by η1-BF4−. Structures of the compounds 2 (M = Ru, L = dppe), trans-[RuH(CNBF3)(dppe)2] and 2* (M = Os, L = dppe) are reported. The CNH ligand is a good hydrogen-bond donor so that NH⋯O or NH⋯F hydrogen bonds with the counter ion are formed. The reaction of BPh4− with the CNH ligand of 2 (M = Ru, L = dppe) produces trans-[Ru(H)(CNBPh3)(dppe)2], the structure of which is reported. Therefore the CNH ligand reacts readily with BX4− (X = F or Ph) to produce CNBX3− ligands and HX.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.003 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 it