Nickel(II) and Palladium(II) Bis-Aminophosphine Pincer Complexes
Bibliographic record
Abstract
The aminophosphine ligands CH 2 (CH 2 NHP t Bu 2 ) 2 ( 1 ), (CH 2 NHP t Bu 2 ) 2 ( 2 ), and (CH 2 NMeP t Bu 2 ) 2 ( 3 ) were prepared from the corresponding amines and ClP t Bu 2 . The ligand 1 reacts with PdI 2 to give the pincer complex (κ 3 P,C,P -CH(CH 2 NHP t Bu 2 ) 2 )PdI ( 4 ). The analogous reaction of 1 with NiCl 2 (dme) gave a the purple product (κ 3 P,N,P - t Bu 2 PNH(CH 2 ) 3 NP t Bu 2 )NiCl ( 5 ), which contains a strained three-membered P–N–Ni ring. Subsequent reaction of 5 with B(C 6 F 5 ) 3 resulted in conversion to (κ 3 P,C,P -CH(CH 2 NHP t Bu 2 ) 2 )NiCl ( 6 ). The related reaction of the aminophosphine ligand 2 with PdI 2 and with NiCl 2 (dme) led, in both cases, to the complexes (κ 3 P,N,P - t Bu 2 PNH(CH 2 ) 2 NP t Bu 2 )MX (MX = PdI ( 7 ), NiCl ( 8 )), respectively, whereas the reaction of 3 with PdX 2 gave (κ 3 P,C,P- t Bu 2 PN(Me)CHCH 2 N(Me)P t Bu 2 )PdX (X = I ( 9 ), Br ( 10 ), Cl ( 11 )). The analogous reaction of 3 with NiCl 2 (dme) afforded [(tBu 2 PH)(NMe)(CH 2 ) 2 (NMe)(tBu 2 P)NiCl 3 ], ( 12 ), which upon treatment with B(C 6 F 5 ) 3 afforded the species (κ 3 P,C,P - t Bu 2 PN(Me)CHCH 2 N(Me)P t Bu 2 )NiCl ( 13 ). Crystallographic studies of 4 – 6, 8, 9, 11, and 12 are reported. The implications of these results are considered.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.141 | 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".