Rhodium(III)-Cyclometalated-Imine Complexes: Solution Behavior and Reactivity with Molecular Hydrogen
Bibliographic record
Abstract
Acetone solutions of cis,trans,cis -[Rh(H) 2 (PPh 3 ) 2 (acetone) 2 ]PF 6 and cis -[Rh(PPh 3 ) 2 (acetone) 2 ]PF 6 react with the imines RN CR‘(R‘ ‘), where R = PhCH 2, Ph, or C 6 H 11; R‘ = H or Me; and R‘ ‘ = Ph or p -OMe-C 6 H 4, to form orthometalated complexes exemplified by [Rh(H){RN CR‘( o -C 6 H 4 )}(PPh 3 ) 2 (acetone)]PF 6 that are generally characterized spectroscopically, and in one case (where R = PhCH 2, R‘ = Me, and R‘ ‘ = p -OMe-C 6 H 4 ) by X-ray crystallography. These complexes maintain their integrity in acetone solution and show no reaction toward 1 atm H 2 at ambient conditions. In MeOH, the complexes in which R‘ = Me simply change to the corresponding MeOH derivative, but when R‘ = H they are partially converted to the non-orthometalated, η 1 -N-imine species [Rh(PPh 3 ) 2 (RN CHR‘ ‘)(MeOH)]PF 6 ( I ), and in MeOH, stoichiometric hydrogenation of the imine to the corresponding amine occurs via I . We have shown recently ( Inorg. Chem. 2004, 43, 4820) that the catalyzed hydrogenation of PhCH 2 N C(H)Ph to dibenzylamine using cis,trans,cis -[Rh(H) 2 (PPh 3 ) 2 (MeOH) 2 ]PF 6 as catalyst precursor in MeOH proceeds via a cationic Rh-( η 1 - N -imine)(amine) intermediate ( II ), analogous to I but with the MeOH replaced by the amine that is formed via hydrolysis of the imine by the presence of adventitious water. Intermediate I (R = PhCH 2, R‘ ‘ = Ph) is shown to be somewhat less active than II toward H 2, but both intermediates provide viable pathways for hydrogenation of the imine. The orthometalated imine-amine complex [Rh(H){PhCH 2 N C(Me)( o- C 6 H 4 )}(PPh 3 ) 2 (NH 2 CH 2 Ph)]PF 6, where the benzylamine comes from imine hydrolysis, is also isolated and characterized crystallographically.
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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 | 0.001 |
| 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 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".