Structural Similarities in Dinuclear, Tetranuclear, and Pentanuclear Nickel Silyl and Silylene Complexes Obtained via Si–H and Si–C Activation
Bibliographic record
Abstract
The reactions of ( i Pr 3 P) 2 Ni 0 precursors with Ph 2 SiHCl, Ph 2 SiH 2, PhSiH 3, and Ph 3 SiH provide mononuclear, dinuclear, tetranuclear, and pentanuclear complexes with silyl and silylene ligands. Reaction of the dinuclear Ni(0) dinitrogen complex [( i Pr 3 P) 2 Ni] 2 (μ-η 1:η 1 -N 2 ) with Ph 2 SiHCl afforded the thermally sensitive mononuclear complex ( i Pr 3 P) 2 Ni(H)SiClPh 2 ( 1 ), which displays considerable hydridic character in the Ni–H–Si interaction. This species thermally converts to the dinuclear complex [( i Pr 3 P)Ni(μ-SiHPh 2 )] 2 ( 2 ), where the silyl ligand bridges via an agostic Si–H interaction. Alternate higher-yield routes to 2 include the rapid room-temperature reaction of Ph 2 SiH 2 with [( i Pr 3 P) 2 Ni] 2 (μ-η 1:η 1 -N 2 ) and the reaction of Ph 2 SiH 2 with Ni(1,5-cyclooctadiene) 2 and i Pr 3 P at elevated temperatures. Double Si–H activations are observed in the reaction of PhSiH 3 with [( i Pr 3 P) 2 Ni] 2 (μ-η 1:η 1 -N 2 ), which provides the tetranuclear C 3 -symmetric complex ( i Pr 3 P)Ni[( i Pr 3 P)Ni(μ 3 -SiHPh)] 3 ( 3 ) as the major product and the pentanuclear S 4 -symmetric complex Ni[( i Pr 3 P)Ni(μ 3 -SiHPh)] 4 ( 4 ) as a minor product. Density functional theory (DFT) geometry optimizations of model complexes support the presence of agostic Ni–H–Si interactions within the tetra- and pentanuclear cores of 3 and 4 . The reaction of Ph 3 SiH with [( i Pr 3 P) 2 Ni] 2 (μ-η 1:η 1 -N 2 ) results in Si–C bond cleavage to provide the asymmetric dinuclear complex [( i Pr 3 P) 2 Ni] 2 (μ-C 6 H 5 )(μ-SiHPh 2 ) ( 5 ), where the phenyl moiety is asymmetrically bridging. Complexes 2 – 5 all display similar coordination environments at one of the nickel centers, suggestive of formal oxidation state assignments of Ni(III)–Ni(I) in tetranuclear 3 and Ni(IV)–Ni(I) in pentanuclear 4 .
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".