Radicalizing CO by mononuclear palladium(I)

A mononuclear, T-shaped palladium(I) d9 metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd−C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structu...

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Bibliographic Details
Main Authors: Bruckhoff, Tim (Author) , Ballmann, Joachim (Author) , Gade, Lutz H. (Author)
Format: Article (Journal) Editorial
Language:English
Published: May 6, 2024
In: Angewandte Chemie. International edition
Year: 2024, Volume: 63, Issue: 19, Pages: 1-6
ISSN:1521-3773
DOI:10.1002/anie.202320064
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/anie.202320064
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202320064
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Author Notes:Tim Bruckhoff, Joachim Ballmann, and Lutz H. Gade
Description
Summary:A mononuclear, T-shaped palladium(I) d9 metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd−C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X-ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert-butyl) disulfide under homolytic S−S cleavage and C−S bond formation to give the corresponding metallathioester.
Item Description:Online verfügbar: 18. März 2024, Version des Artikels online: 4. April 2024
Gesehen am 26.07.2024
Physical Description:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.202320064