Synthesis and Reactivity of Ruthenium Hydride Complexes Containing a Tripodal Aminophosphine Ligand
Bibliographic record
Abstract
Ru complexes containing a tris(aminophosphine) ligand (N(NP) 3 ) have been prepared and their reactivity examined. The complex [(N((CH 2 ) 2 NHP i Pr 2 ) 2 (κ 2 N, P -((CH 2 ) 2 NHP i Pr 2 ))RuCl][Cl] ( 1 ) is transformed to [(N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 NPH i Pr 2 ))RuCl]Cl ( 2 ) on standing in solution. Deprotonation of the phosphonium center in 2 followed by anion exchange generates the Ru hydride complex [(N((CH 2 ) 2 NHP i Pr 2 )((CH 2 ) 2 NP i Pr 2 )(CH 2 CHNHP i Pr 2 ))RuH][BPh 4 ] ( 3 ), which can bind acetonitrile to give [(N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 NP i Pr 2 ))Ru(CH 3 CN)][BPh 4 ] ( 5 ). Protonation of 3 and 5 with either a 1 M solution of HCl in diethyl ether or NEt 3 HCl yields [(N((CH 2 ) 2 NHPiPr 2 ) 2 ((CH 2 ) 2 NPHiPr 2 ))RuCl][BPh 4 ] ( 6 ). Reaction of 3 with H 2 gives the Ru hydride complex [(N((CH 2 ) 2 NHP i Pr 2 ) 2 (κ 2 N, P ((CH 2 ) 2 NHP i Pr 2 ))RuH][BPh 4 ] ( 8 ), which is deprotonated with KN(SiMe 3 ) 2 to give [(N((CH 2 ) 2 NHP i Pr 2 ) 2 )((CH 2 ) 2 NP i Pr 2 )RuH] ( 9 ). This latter species reacts with H 2 to generate [(N((CH 2 ) 2 NHP i Pr 2 ) 3 )Ru(H) 2 ] ( 10 ). The hydride species 3 is also shown to react with CO 2, N 2 O, phenylacetylene, and 1-pentyne to give [(N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 NP(CO 2 ) i Pr 2 ))Ru][BPh 4 ] ( 11 ), [(N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 NP(O) i Pr 2 ))Ru][BPh 4 ] ( 12 ), and [(N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 NP(R) i Pr 2 ))Ru][BPh 4 ] (R = C 8 H 6 ( 13 ), C 5 H 10 ( 14 )), in which the substrate is bound to P and the metal center. In contrast, 9 does not react with N 2 O and alkyne but reacts with CO 2 to give CO 2 insertion into the N–P bond, yielding (N((CH 2 ) 2 NHP i Pr 2 ) 2 ((CH 2 ) 2 N(CO 2 )P i Pr 2 )RuH ( 15 ).
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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 | 0.001 |
| 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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".