Trifluoromethyl-Substituted Benzocyclobutenone and Benzocyclobutenedione: The Structure Anomaly of (Benzocyclobutenedione)tricarbonylchromium Complexes

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 π orbitals of the arene ring toward the tricarbonylchromium group.

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

“…We anticipated that the protocol could also be used for the synthesis of 9,10-phenanthrenequinone ( 3t ) and benzocyclobutene-1,2-dione ( 3u ), the compounds that have found wide applications in organic synthesis and many other areas. , To this end, diazo precursors 1t and 1u were first prepared from either ethyl 2-bromobenzoate in a three-step sequence ( 7 → 8 → 1t ), or commercially available 1,3-indanedione by a single diazo transfer reaction (Scheme ). In comparison to the 1,3-diaryl-2-diazo-1,3-diketone system, the decomposition of 1t / u to 3t / u turned out to be more formidable presumably owing to unfavorable strain and rigidity of the ketene intermediates.…”