Details
| Original language | English |
|---|---|
| Pages (from-to) | 3039-3052 |
| Number of pages | 14 |
| Journal | Organometallics |
| Volume | 38 |
| Issue number | 15 |
| Publication status | Published - 1 Aug 2019 |
Abstract
The syntheses of methoxy- and trifluoromethyl-substituted benzocyclobutenone and benzocyclobutenedione tricarbonylchromium complexes are described. As with the unsubstituted complex, a route via the respective acetals was used. However, attempts to hydrolyze rac-tricarbonyl[1,2-bis(ethylenedioxy)-3-(trifluoromethyl)benzocyclobutene]chromium(0) (rac-12) resulted in only a single hydrolysis and led to rac-tricarbonyl{η6-[2-(ethylendioxy)-3-(trifluoromethyl)benzocyclobutenone]}chromium(0) (rac-14) with different regioselectivity in comparison to the respective reaction of the methoxy-substituted derivative. The synthesis of the desired rac-tricarbonyl[3-(trifluoromethyl)benzocyclobutenedione]chromium(0) (rac-13) was finally achieved by a route via an acyclic diacetal. Compounds were characterized spectroscopically and in a number of cases also by crystal structure analyses. The unusual bending of the annelated cyclobutenedione ring toward the tricarbonylchromium moiety was observed for rac-tricarbonyl-[η6-(methoxybenzocyclobutenedione)chromium(0) (rac-4) as well. To gain more insight into the unusually large bending of the annelated cyclobutenedione or cyclobutenone rings toward the tricarbonylchromium group in some of the studied compounds, we also performed density functional theory (DFT) calculations. In general, the gas-phase DFT optimized structure parameters show good agreement with the crystal structure data, indicating that the cyclobutenedione or cyclobutenone ring bending is a molecular rather than a crystal-packing effect. The DFT optimized structure data also show that annelated cyclobutenedione rings bend more strongly toward the tricarbonylchromium group than do their cyclobutenone analogues. Moreover, the staggered conformation of the tricarbonylchromium group favors larger bending angles. Topological analyses of the electron density of the studied (arene)tricarbonylchromium complexes suggest that the cyclobutenedione ring bending originates from the bending of πorbitals of the arene ring toward the tricarbonylchromium group.
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
- Chemistry(all)
- Inorganic Chemistry
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In: Organometallics, Vol. 38, No. 15, 01.08.2019, p. 3039-3052.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Trifluoromethyl-Substituted Benzocyclobutenone and Benzocyclobutenedione
T2 - The Structure Anomaly of (Benzocyclobutenedione)tricarbonylchromium Complexes
AU - Böning (née Pfennig), Monika
AU - Dongol, Krishna Gopal
AU - Romero Boston, Geanne Marize
AU - Schmitz, Stefan
AU - Wartchow, Rudolf
AU - Samaniego-Rojas, Juan D.
AU - Köster, Andreas M.
AU - Butenschön, Holger
N1 - Funding information: This research was kindly supported by the Gottlieb Daimler- and Karl Benz-Foundation (doctoral fellowship to K.G.D.) and by the Deutsche Forschungsgemeinschaft (BU 814/7-1, 7-2). We are indebted to Dr. Michael Wiebcke, Institut für Anorganische Chemie, Leibniz Universität Hannover, for help with a crystallographic analysis. J.D.S.-R. gratefully acknowledges a CONACyT Ph.D. fellowship (490270). The research at Cinvestav was supported by the SEP-Cinvestav project 65 and the CONACyT project GIC 268251.
PY - 2019/8/1
Y1 - 2019/8/1
N2 - The syntheses of methoxy- and trifluoromethyl-substituted benzocyclobutenone and benzocyclobutenedione tricarbonylchromium complexes are described. As with the unsubstituted complex, a route via the respective acetals was used. However, attempts to hydrolyze rac-tricarbonyl[1,2-bis(ethylenedioxy)-3-(trifluoromethyl)benzocyclobutene]chromium(0) (rac-12) resulted in only a single hydrolysis and led to rac-tricarbonyl{η6-[2-(ethylendioxy)-3-(trifluoromethyl)benzocyclobutenone]}chromium(0) (rac-14) with different regioselectivity in comparison to the respective reaction of the methoxy-substituted derivative. The synthesis of the desired rac-tricarbonyl[3-(trifluoromethyl)benzocyclobutenedione]chromium(0) (rac-13) was finally achieved by a route via an acyclic diacetal. Compounds were characterized spectroscopically and in a number of cases also by crystal structure analyses. The unusual bending of the annelated cyclobutenedione ring toward the tricarbonylchromium moiety was observed for rac-tricarbonyl-[η6-(methoxybenzocyclobutenedione)chromium(0) (rac-4) as well. To gain more insight into the unusually large bending of the annelated cyclobutenedione or cyclobutenone rings toward the tricarbonylchromium group in some of the studied compounds, we also performed density functional theory (DFT) calculations. In general, the gas-phase DFT optimized structure parameters show good agreement with the crystal structure data, indicating that the cyclobutenedione or cyclobutenone ring bending is a molecular rather than a crystal-packing effect. The DFT optimized structure data also show that annelated cyclobutenedione rings bend more strongly toward the tricarbonylchromium group than do their cyclobutenone analogues. Moreover, the staggered conformation of the tricarbonylchromium group favors larger bending angles. Topological analyses of the electron density of the studied (arene)tricarbonylchromium complexes suggest that the cyclobutenedione ring bending originates from the bending of πorbitals of the arene ring toward the tricarbonylchromium group.
AB - The syntheses of methoxy- and trifluoromethyl-substituted benzocyclobutenone and benzocyclobutenedione tricarbonylchromium complexes are described. As with the unsubstituted complex, a route via the respective acetals was used. However, attempts to hydrolyze rac-tricarbonyl[1,2-bis(ethylenedioxy)-3-(trifluoromethyl)benzocyclobutene]chromium(0) (rac-12) resulted in only a single hydrolysis and led to rac-tricarbonyl{η6-[2-(ethylendioxy)-3-(trifluoromethyl)benzocyclobutenone]}chromium(0) (rac-14) with different regioselectivity in comparison to the respective reaction of the methoxy-substituted derivative. The synthesis of the desired rac-tricarbonyl[3-(trifluoromethyl)benzocyclobutenedione]chromium(0) (rac-13) was finally achieved by a route via an acyclic diacetal. Compounds were characterized spectroscopically and in a number of cases also by crystal structure analyses. The unusual bending of the annelated cyclobutenedione ring toward the tricarbonylchromium moiety was observed for rac-tricarbonyl-[η6-(methoxybenzocyclobutenedione)chromium(0) (rac-4) as well. To gain more insight into the unusually large bending of the annelated cyclobutenedione or cyclobutenone rings toward the tricarbonylchromium group in some of the studied compounds, we also performed density functional theory (DFT) calculations. In general, the gas-phase DFT optimized structure parameters show good agreement with the crystal structure data, indicating that the cyclobutenedione or cyclobutenone ring bending is a molecular rather than a crystal-packing effect. The DFT optimized structure data also show that annelated cyclobutenedione rings bend more strongly toward the tricarbonylchromium group than do their cyclobutenone analogues. Moreover, the staggered conformation of the tricarbonylchromium group favors larger bending angles. Topological analyses of the electron density of the studied (arene)tricarbonylchromium complexes suggest that the cyclobutenedione ring bending originates from the bending of πorbitals of the arene ring toward the tricarbonylchromium group.
UR - http://www.scopus.com/inward/record.url?scp=85071313600&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.9b00370
DO - 10.1021/acs.organomet.9b00370
M3 - Article
AN - SCOPUS:85071313600
VL - 38
SP - 3039
EP - 3052
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 15
ER -