Nickel and Palladium Complexes of Ferrocene-Backbone Bisphosphine-Borane and Trisphosphine Ligands
Bibliographic record
Abstract
Reaction of a ferrocene-backbone bisphosphine-borane ligand, [Fe(η 5 -C 5 H 4 PPh 2 )(η 5 -C 5 H 4 P t Bu{C 6 H 4 (BPh 2 )- o })] (FcPPB), with [Ni(cod) 2 ] (cod = 1,5-cyclooctadiene) or 0.5 equiv of [Pd 2 (dba) 3 ] (dba = trans, trans -dibenzylideneacetone) afforded [Ni(FcPPB)] ( 1 ) and [Pd(FcPPB)] ( 2 ), respectively; compound 1 does not react with dba. The FcPPB ligand in complexes 1 and 2 is coordinated via both phosphine donors and an η 3 BCC -interaction with boron and the ipso - and ortho -carbon atoms of a B -phenyl group. The triphosphine analogue of the FcPPB ligand, [Fe(η 5 -C 5 H 4 PPh 2 )(η 5 -C 5 H 4 P t Bu{C 6 H 4 (PPh 2 )- o })] (FcPPP), was prepared by lithiation of [Fe(η 5 -C 5 H 4 PPh 2 )(η 5 -C 5 H 4 P t Bu(C 6 H 4 Br- o )] followed by addition of Ph 2 PCl, and reaction of FcPPP with [Ni(cod) 2 ] provided “Ni(FcPPP)” ( 3 ), which exists as a mixture of isomers in which the FcPPP ligand is κ 3 PPP -coordinated. Attempts to obtain X-ray quality crystals of 3 were derailed by its propensity to react with traces of N 2 within an argon-filled glovebox, yielding rac -[{Ni(FcPPP)} 2 (μ-N 2 )] ( 4 ), in which two nickel(0) centers are linked by an end-on-bridging N 2 unit. By contrast, reaction of FcPPP with 0.5 equiv of [Pd 2 (dba) 3 ] provided [Pd(η 2 -dba)(FcPPP)] ( 5 ), in which the FcPPP ligand is κ 2 PP -coordinated, and 1 equiv of dba remains η 2 CC -coordinated to palladium. Complexes 3 and 4 also reacted with dba, forming a new compound tentatively assigned as [Ni(η 2 -dba)(FcPPP)] ( 6 ). Complexes 1, 2, and 5 did not react with N 2 .
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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 | 0.000 |
| 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".