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Verfasst von:Mulks, Florian [VerfasserIn]   i
 Hashmi, A. Stephen K. [VerfasserIn]   i
 Faraji, Shirin [VerfasserIn]   i
Titel:Sesquicarbene complexes
Titelzusatz:Bonding at the interface between M-C single bonds and M═C double bonds
Verf.angabe:Florian F. Mulks, A. Stephen K. Hashmi, and Shirin Faraji
E-Jahr:2020
Jahr:May 7, 2020
Umfang:10 S.
Fussnoten:Gesehen am 27.07.2020
Titel Quelle:Enthalten in: Organometallics
Ort Quelle:Washington, DC : ACS Publ., 1982
Jahr Quelle:2020
Band/Heft Quelle:39(2020), 10, Seite 1814-1823
ISSN Quelle:1520-6041
Abstract:Allylic dimetalated complexes [M2C(vinyl)]+ (M = Au(IPr) and Cr(CO)5−) incorporate a new coordination mode of carbon. Digold complexes of this type have recently been detected experimentally. The intrinsic bond orbitals, partial charges, and structural parameters of the gold complexes and of chromium analogs were studied computationally and compared to those of the respective monometalated species and hydrocarbons. This showed that such digold complexes have a carbene character at both Au−C bonds comparable to typical carbene complexes of gold. Dichromium complexes with their stronger π-backdonation compete for interaction with carbon’s π-orbital; each of the chromium atoms partakes in double bonding that is significant but weaker than that in the carbene analogs. Containing two M−C bonds on the interface between single and double bonds, these bridged complexes can be conceived as “sesquicarbene complexes”. The π-system acted in a very adaptive manner and employed additional stabilization of the vinyl system only where needed. Significant carbene character is found simultaneously in both M−C bonds at the same carbon center. The discovery of these complexes with relatively strong double bond character between one carbon and two metal atoms could bring unusual single-carbon-centered organometallic cascade reactions to the horizon.
DOI:doi:10.1021/acs.organomet.0c00102
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext ; Verlag: https://doi.org/10.1021/acs.organomet.0c00102
 Volltext: https://pubs.acs.org/doi/10.1021/acs.organomet.0c00102
 DOI: https://doi.org/10.1021/acs.organomet.0c00102
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1725570459
Verknüpfungen:→ Zeitschrift

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