Toward Highly Metallized Polymers: Synthesis and Characterization of Silicon-Bridged [1]Ferrocenophanes with Pendent Cluster Substituents
Bibliographic record
Abstract
The acetylide-substituted sila[1]ferrocenophanes [Fe(η-C 5 H 4 ) 2 Si(Me)C⋮CR] (R = Ph ( 2a ), n Bu ( 2b )) reacted with [Co 2 (CO) 8 ], [{MoCp(CO) 2 } 2 ], or [Ni(cod) 2 ]/L selectively at the triple bond to give pendent organocobalt [Fe(η-C 5 H 4 ) 2 Si(Me){Co 2 (CO) 6 C 2 R}] (R = Ph ( 4a ), n Bu ( 4b )) or organomolybdenum [Fe(η-C 5 H 4 ) 2 Si(Me){Mo 2 Cp 2 (CO) 4 C 2 Ph}] ( 9 ) clusters or mononuclear organonickel [Fe(η-C 5 H 4 ) 2 Si(Me){Ni(L)C 2 Ph}] (L = dmpe ( 11 ), L = dppe ( 12 )) complexes. The bis(acetylide)-substituted sila[1]ferrocenophanes [Fe(η-C 5 H 4 ) 2 Si(C⋮CR) 2 ] (R = n Bu ( 6a ), Ph ( 6b )) reacted with [Co 2 (CO) 8 ] in an analogous fashion, forming the novel pentametallic silicon-bridged [1]ferrocenophanes with two pendent cobalt clusters [Fe(η-C 5 H 4 ) 2 Si{Co 2 (CO) 6 C 2 R} 2 ] (R = n Bu ( 7a ), R = Ph ( 7b )). Compound 7b subsequently underwent rapid hydrolytic ring-opening to yield an unusual, highly metallized silanol, [(η-C 5 H 5 )Fe(η-C 5 H 4 )Si(OH){Co 2 (CO) 6 C 2 Ph} 2 ] ( 8b ). This reaction was found to be much slower for the hexynyl analogue ( 7a ). The organonickel complexes ( 11 and 12 ) described in this work represent the first examples of mononuclear complexes prepared directly from an alkyne and [Ni(cod) 2 ]. We postulate that steric factors prevent the addition of a second nickel fragment to the alkyne. The synthesis of a sila[1]ferrocenophane with a pendent platinum moiety was also attempted. However, reaction of 2a with [Pt(PEt 3 ) 3 ] instead gave the platinasila[2]ferrocenophane [Fe(η-C 5 H 4 ) 2 Pt(PEt 3 ) 2 Si(Me)C⋮CPh] ( 15 ) via oxidative insertion of the platinum(0) fragment into a strained ipso -cyclopentadienyl carbon−silicon bond of the sila[1]ferrocenophane.
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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) | 0.006 | 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 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".