Hybrid Bicyclo[1.1.0]butanes [(R 4 Si 3 )CH 2 ] and [(R 4 Si 2 Ge)CH 2 ] (R = SiMe t Bu 2 ): Synthesis and Thermal Isomerization to Alkyl-Substituted Cyclopropenes [R 3 Si 3 ]CH 2 R and [R 3 Si 2 Ge]CH 2 R - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2023

Hybrid Bicyclo[1.1.0]butanes [(R 4 Si 3 )CH 2 ] and [(R 4 Si 2 Ge)CH 2 ] (R = SiMe t Bu 2 ): Synthesis and Thermal Isomerization to Alkyl-Substituted Cyclopropenes [R 3 Si 3 ]CH 2 R and [R 3 Si 2 Ge]CH 2 R

Résumé

Hybrid bicyclo[1.1.0]butanes comprised of different group 14 elements, namely, 1,2,3-trisilabicyclo[1.1.0]butane and 1,3-disila-2-germabicyclo[1.1.0]butane, were readily prepared by the reductive dichlorination of 1,3-dichlorocyclobutane precursors. Both compounds feature exceptionally short bridging Si–Si bonds and practically planar geometry around the bridging Si atoms, thus representing a novel structural motif in the chemistry of the heavy analogues of bicyclo[1.1.0]butanes. These peculiar structures were explained by the steric interaction between the substituents at the bridging and bridgehead positions. Thermolysis of the title bicyclo[1.1.0]butanes in toluene at 130 °C resulted in their isomerization to the alkyl-substituted cyclopropene analogues. The mechanism of this isomerization was revealed in detail on the basis of deuterium-labeled experiments, kinetic investigations, trapping experiments, and computational studies to establish the nature of the key intermediate of the whole isomerization process.
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hal-04175751 , version 1 (02-08-2023)

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Vladimir Ya. Lee, Hiroyuki Yasuda, Olga Gapurenko, Ruslan Minyaev, Heinz Gornitzka, et al.. Hybrid Bicyclo[1.1.0]butanes [(R 4 Si 3 )CH 2 ] and [(R 4 Si 2 Ge)CH 2 ] (R = SiMe t Bu 2 ): Synthesis and Thermal Isomerization to Alkyl-Substituted Cyclopropenes [R 3 Si 3 ]CH 2 R and [R 3 Si 2 Ge]CH 2 R. Organometallics, In press, 42 (18), pp.2514-2521. ⟨10.1021/acs.organomet.2c00599⟩. ⟨hal-04175751⟩
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