CpCo-stabilized cyclopentadienones from cyclobutadiene complexes: experimental and theoretical investigations
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 tetrathiaalk...
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| Main Authors: | , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
03/23/2005
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| In: |
Organometallics
Year: 2005, Volume: 24, Issue: 9, Pages: 2106-2113 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om050048r |
| Online Access: | Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1021/om050048r Verlag, lizenzpflichtig, Volltext: https://pubs.acs.org/doi/10.1021/om050048r 
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| Author Notes: | Carsten Schaefer, Daniel B. Werz, Tobias H. Staeb, Rolf Gleiter, and Frank Rominger |
| Summary: | 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. |
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| Item Description: | Gesehen am 11.11.2020 |
| Physical Description: | Online Resource |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/om050048r |