Complexes of phosphine–phenolate ligands with the [Reî€O]3+ and [Re(HNNC5H4N)(NNC5H4N)]2+ cores
Bibliographic record
Abstract
Complexes incorporating the [ReO]3+ core have been synthesised with ligands containing the new methyl substituted phosphine–phenolate PO and PO2 donor sets, (2-hydroxy-5-methylphenyl)diphenylphosphine (H(MePO)) and bis(2-hydroxy-5-methylphenyl)phenylphosphine (H2(Me2PO2)). The analogous tert-butyl ligands, (5-tert-butyl-2-hydroxyphenyl)diphenylphosphine (H(t-BuPO)) and bis(5-tert-butyl-2-hydroxyphenyl)phenylphosphine (H2(t-Bu2PO2)), were also prepared. Reaction of either mer-[ReOCl3(PPh3)2] or [NH4][ReO4] in CH3OH with H(MePO) led to formation of [ReOCl(MePO)2] (1) in good yield. Reaction of [NH4][ReO4] with H2(Me2PO2) in CH3OH afforded [ReO(Me2PO2)(H(Me2PO2))] (2), also in good yield. X-Ray crystallographic analyses of 1 and 2 demonstrated that both complexes are neutral and octahedral, and contain the oxo moiety. Two complexes have been structurally characterised from the reaction of (o-hydroxyphenyl)diphenylphosphine (HPO) with [Re(Hhypy)(hypyH)Cl3]: [Re(Hhypy)(hypy)(PO)(HPO)]Cl (3) and [ReCl(Hypy)(hypy)(PO)] (4) (hypy = NNC5H4N, Hhypy = HNNC5H4N, hypyH = NNC5H4NH). X-Ray crystallography demonstrated that both are Re(III) complexes; 3 is monocationic with an N3OP2 coordination sphere while 4 is neutral with a ClN3OP coordination sphere. [Re(Hhypy)(hypy)(HPO2)(H2PO2)]Cl (5) and [Re(Hhypy)(hypy)(H(Me2PO2))(H2(Me2PO2))]Cl (6) were synthesised by reaction of [Re(Hhypy)(hypyH)Cl3] in CH3OH with bis(o-hydroxyphenyl)phenylphosphine (H2PO2) and H2(Me2PO2) respectively. Compounds 5 and 6 were shown by 1H and 31P NMR spectroscopies to have the same N3OP2 coordination sphere as [Re(Hhypy)(hypy)(PO)(HPO)]Cl, with the addition of several uncoordinated, protonated phenolic donors.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".