The Dynamic Indium-Bridged [1.1]Ferrocenophane [(Me<sub>2</sub>Ntsi)In(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>Fe]<sub>2</sub>
Bibliographic record
Abstract
Salt metathesis reaction between Li(thf)(Me 2 Ntsi) [Me 2 Ntsi = C(SiMe 3 ) 2 SiMe 2 NMe 2 ] and InX 3 gave the new indium dihalides (Me 2 Ntsi)InX 2 [X = Cl ( 2a ), I ( 2b ); isolated yields 34% ( 2a ) and 44% ( 2b )]. Single-crystal X-ray analysis revealed that 2a is a Cl-bridged dimer, while 2b is monomeric. Salt metathesis reaction between dilithioferrocene and 2a and 2b, respectively, gave the new indium-bridged [1.1]ferrocenophane [(Me 2 Ntsi)In(η 5 -C 5 H 4 ) 2 Fe] 2 ( 3 ). Only when 2a was used, could analytically pure 3 be isolated (45%). Revealed by a single-crystal X-ray analysis, compound 3 crystallized as an anti isomer ( C i symmetry). The diinda[1.1]ferrocenophane 3 showed fluxional behavior in solution. The proton NMR spectrum of 3 revealed only five singlets at ambient temperature (500 MHz, 25 °C, C 6 D 6 or C 7 D 8 ): one singlet for SiMe 2, SiMe 3, and NMe 2 each and two singlets for the 16 Cp protons. These facts can be rationalized by assuming a fast degenerate isomerization from one anti isomer to another anti isomer (time-averaged D 2 h symmetry). The two singlets at 4.43 and 4.45 ppm (500 MHz, 25 °C, C 7 D 8 ) of the α- and β-protons broadened at lower temperature and coalesced at 5 °C. By lowering the temperature further, two sets of signals emerged and became clearly visible at −30 °C, with each set consisting of four singlets for the Cp protons of equal intensity. Consistent with the splitting of the Cp signals, all other signals split in two sets of three singlets, indicating C s symmetric Me 2 Ntsi moieties. These data show that the [1.1]ferrocenophane 3 exists as a mixture of two isomers in toluene solutions (2:1 ratio at −30 °C). Assuming that the thermodynamically favored isomer was found in the crystal lattice, the most intense set of signals was assigned to the anti isomer of 3, while the less intense set of signals was assigned to a syn isomer. The already known diinda[1.1]ferrocenophane {[2-(Me 2 NCH 2 )C 6 H 4 ]In(η 5 -C 5 H 4 ) 2 Fe} 2 ( 1c ) was revisited. Compound 1c did not reveal any fluxional behavior in 1D 1 H NMR spectra at ambient temperature, but EXSY spectroscopy revealed an occurring anti -to- anti isomerization of 1c in solution. A cyclic voltammogram of 3 in thf/0.1 M [Bu 4 N][PF 6 ] showed only an irreversible oxidation. A rationale is given why the reaction of (Me 2 Ntsi)InX 2 [X = Cl ( 2a), I ( 2b )] with dilithioferrocene gave a [1.1]ferrocenophane, as similar reactions of (Me 2 Ntsi)ECl 2 (E = Al, Ga) with dilithioferrocene gave strained [1]ferrocenophanes.
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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 | 0.003 | 0.002 |
| Meta-epidemiology (narrow) | 0.005 | 0.005 |
| Meta-epidemiology (broad) | 0.005 | 0.003 |
| Bibliometrics | 0.002 | 0.008 |
| Science and technology studies | 0.003 | 0.002 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.006 | 0.003 |
| Research integrity | 0.003 | 0.004 |
| Insufficient payload (model declined to judge) | 0.001 | 0.006 |
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; both teacher heads agree on what is shown here.
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".