Synthesis and Crystallographic Characterization of New Manganese(I) Complexes of Donor-Functionalized Indenes
Bibliographic record
Abstract
Treatment of 1-P i Pr 2 -2-NMe 2 -indene ( 2 [H]) with BrMn(CO) 5 provided κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 3 Br ( 4 ) in 73% yield. Addition of either AgBF 4 or AgSO 3 CF 3 to 4 yielded the corresponding inner-sphere tetrafluoroborate ( 5a ) and triflate ( 5b ) complexes in 62% and 65% yield, respectively. Deprotonation of 4, 5a, or 5b produced an intractable mixture of products. The cationic complex [κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 4 ] + BF 4 - ( 6 ) was prepared in 30% yield by treating BrMn(CO) 5 with AgBF 4, followed by the addition of 2 [H]. The benzocymantrene η 5 -[ 2 ]Mn(CO) 3 was prepared in 56% yield via reduction of η 5 -(2-NMe 2 -3-P(S) i Pr 2 -indenyl)Mn(CO) 3 with Cl 3 SiSiCl 3 . Compound 2 [Li] reacts with BrMn(CO) 5 to give a complex product mixture, from which 4 and [κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 4 ] + [Mn 2 (CO) 8 (μ-P i Pr 2 )] - ( 7 ) were isolated. 2-Dimethylaminoindene ( 1 [H]) was silylated to give 1-SiMe 3 -2-NMe 2 -indene ( 8 [H]) in 93% yield. Treatment of 8 [Li] with ClP i Pr 2, followed by the addition of BrMn(CO) 5, afforded κ 2 - P, N -(1-SiMe 3 -2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 3 Br ( 10 ) in 27% yield. Alternatively, addition of 8 [Li] to BrMn(CO) 5 followed by the addition of ClP i Pr 2 generated a mixture of products, from which the substituted 1,1‘-biindene rac -(2-NMe 2 -3-SiMe 3 -C 9 H 5 ) 2 ( rac - 12 ) was isolated. Treatment of 1 [Li] with BrMn(CO) 5 provided η 5 -(2-NMe 2 -indenyl)Mn(CO) 3 ( 11 ) in 41% yield. Single-crystal X-ray diffraction data for 4 ·0.5C 7 H 8, 5a ·0.5C 7 H 8, 5b, 6, η 5 -[ 2 ]Mn(CO) 3, 7 ·0.5C 7 H 8, 10, 11, and rac - 12 are reported.
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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 | 0.001 |
| 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) | 0.040 | 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".