CpCo-stabilized cyclopentadienones from cyclobutadiene complexes

• Verfasst von: Schaefer, Carsten [VerfasserIn]
• Verfasst von: Werz, Daniel B. [VerfasserIn]
• Verfasst von: Stäb, Tobias [VerfasserIn]
• Verfasst von: Gleiter, Rolf [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Titel: CpCo-stabilized cyclopentadienones from cyclobutadiene complexes
• Titelzusatz: experimental and theoretical investigations
• Verf.angabe: Carsten Schaefer, Daniel B. Werz, Tobias H. Staeb, Rolf Gleiter, and Frank Rominger
• E-Jahr: 2005
• Jahr: 03/23/2005
• Umfang: 8 S.
• Fussnoten: Gesehen am 11.11.2020
• Titel Quelle: Enthalten in: Organometallics
• Ort Quelle: Washington, DC : ACS Publ., 1982
• Jahr Quelle: 2005
• Band/Heft Quelle: 24(2005), 9, Seite 2106-2113
• ISSN Quelle: 1520-6041
• DOI: doi:10.1021/om050048r
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 173839266X

Abstract

The reaction of 1,4,8,11-tetrathiacyclotetradeca-2,9-diyne (7) with C5H4(CO2Me)Co(CO)2 (8) and C5H4(SiMe3)Co(CO)2 (10) led to the tricyclic cyclopentadienone complexes 9 and 11. In both species the CO was inserted into a former triple bond. This observation led to the preparation of the tetrathiaalkyl- and tetrathiaaryl-substituted C5H4(CO2Me)Co-capped cyclobutadiene complexes 23 and 27−30. When these compounds were heated under a pressurized CO atmosphere at 170 °C, the corresponding cyclopentadienone complexes 9, 15, and 31−33 were formed. Model calculations at the B3LYP level of theory on tetrasubstituted (R = CH3, SH, (CH2)3, S−CH2−S) CpCo-capped cyclobutadiene complexes showed that the substitution, especially by SH and S−CH2−S, considerably lowered the energy of the assumed intermediate metallacycles 35 and 36, which opens the possibility of reaction.