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In Crystallo Wolff Rearrangement of a Metalated Diazoester: Structural Confirmation of the Singlet Carbene
Ze-Jie Lv1, Arnd Fitterer2, Regine Herbst-Irmer1
1Institut für Anorganische Chemie and International Center for Advanced Studies of Energy Conversion (ICASEC), University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
Abstract:
The Wolff rearrangement (WR) is widely used for the synthesis of ketenes from diazoketones and -esters. Stepwise WR reactions are proposed to proceed through transient carbonylcarbene (R-C-C(O)-R') intermediates, which so far have evaded structural characterization. Here, a Wolff metallocarbene (PtII-C-C(O)-OEt) is reported as a fleeting intermediate in the photoinitiated fragmentation of a diazoester ligand. Frozen solution and crystal matrix isolation experiments enabled the spectroscopic, magnetic, crystallographic, and computational characterization of this highly reactive species. All methods confirmed a singlet ground state for the WR metallocarbene, which is stabilized by π interactions with the carboxyl substituent, thus complementing computational and transient spectroscopy studies for classic organic WR reactions.
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