Synthesis and chemistry of bis(triisopropylphosphine) nickel(<scp>i</scp>) and nickel(0) precursors
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Bibliographic record
Abstract
High yield syntheses of ((i)Pr(3)P)(2)NiX (3a-c), (where X = Cl, Br, I) were established by comproportionation of ((i)Pr(3)P)(2)NiX(2) (1a-c) with ((i)Pr(3)P)(2)Ni(η(2)-C(2)H(4)) (2). Reaction of 1a with either NaH or LiHBEt(3) provided ((i)Pr(3)P)(2)NiHCl (4), along with 3a as a side-product. Reduction of ((i)Pr(3)P)(2)NiCl (3a-c) with Mg in presence of nitrogen saturated THF solutions provided the dinitrogen complex [((i)Pr(3)P)(2)Ni](2)(μ-η(1):η(1)-N(2)) (5). In aromatic solvents such as benzene and toluene a thermal equilibrium exists between 5 and the previously reported monophosphine solvent adducts ((i)Pr(3)P)Ni(η(6)-arene) (6a,b). Reaction of 5 with carbon dioxide provided ((i)Pr(3)P)(2)Ni(η(2)-CO(2)) (7). Thermolysis of 9 at 60 °C provided a mixture of products that included the reduction product ((i)Pr(3)P)(2)Ni(CO)(2) (8) along with (i)Pr(3)P=O, as identified by NMR spectroscopy. Complex 8 was also prepared in high yield from the reaction of 5 with CO. Reaction of 5 with CS(2) gave the dimeric carbon disulfide complex [((i)Pr(3)P)Ni(μ-η(1):η(2)-CS(2))](2) (9). Diphenylphosphine reacts with 5 to form the dinuclear Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-PPh(2))](2) (10). Complex 5 reacts with PhSH to form ((i)Pr(3)P)(2)Ni(SPh)(H) (11), which slowly loses H(2) and (i)Pr(3)P to form the dimeric Ni(I) complex [((i)Pr(3)P)Ni(μ(2)-SPh)](2) (12) at room temperature. Complex 12 was also accessed by salt metathesis from the reaction of ((i)Pr(3)P)(2)NiCl (3a) with PhSLi, which demonstrates the utility of 3a as a Ni(I) precursor. With the exception of 6a,b, all compounds were structurally characterized by single-crystal X-ray crystallography.
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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 | 0.000 | 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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.006 | 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