In Crystallo Wolff Rearrangement of a Metalated Diazoester: Structural Confirmation of the Singlet Carbene Wolff-Intermediate.

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 (Pt^II-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 spectros

SUBMITTER: Lv ZJ 

PROVIDER: S-EPMC11848915 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature