σ0π2 Singlet Ground State Carbenes Undergo Least-Motion Reactions with H2 and Alkenes
Ground state singlet carbenes commonly feature σ2π0 orbital occupations and are known for their concerted σ-bond insertion and cycloaddition reactions. Despite the facility of these transformations, orbital symmetry conservation forces them into non-least-motion π-approach reaction pathways. This si...
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| Veröffentlicht in: | Journal of organic chemistry 2021-11, Vol.86 (21), p.15247-15252 |
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| container_title | Journal of organic chemistry |
| container_volume | 86 |
| creator | Clewing, Stefan F Wagner, J. Philipp |
| description | Ground state singlet carbenes commonly feature σ2π0 orbital occupations and are known for their concerted σ-bond insertion and cycloaddition reactions. Despite the facility of these transformations, orbital symmetry conservation forces them into non-least-motion π-approach reaction pathways. This situation completely changes when the singlet σ0π2 electron configuration becomes the ground state, which we show here by means of high-level CCSD(T) geometry optimizations. Carbenes like the experimentally known 2H-imidazol-2-ylidene react with H2 and ethylene with negligible or no barrier in a σ-fashion, which effectively corresponds to a least-motion reaction trajectory. |
| doi_str_mv | 10.1021/acs.joc.1c01865 |
| format | Article |
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Despite the facility of these transformations, orbital symmetry conservation forces them into non-least-motion π-approach reaction pathways. This situation completely changes when the singlet σ0π2 electron configuration becomes the ground state, which we show here by means of high-level CCSD(T) geometry optimizations. Carbenes like the experimentally known 2H-imidazol-2-ylidene react with H2 and ethylene with negligible or no barrier in a σ-fashion, which effectively corresponds to a least-motion reaction trajectory.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.joc.1c01865</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-1433-0292</orcidid></addata></record> |
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| title | σ0π2 Singlet Ground State Carbenes Undergo Least-Motion Reactions with H2 and Alkenes |
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