A Palladium(II) Peroxido Complex Supported by the Smallest Steric N‐Heterocyclic Carbene, IMe = 1, 3‐Dimethylimidazole‐2‐ylidene, and Its Reactivity by Oxygen‐Atom Transfer. Issue 28 (7th September 2016)

• Record Type: Journal Article
• Authors: Lee, Eunsung; Bae, Dae Young; Park, Sungho; Oliver, Allen G.; Kim, Yonghwi; Yandulov, Dmitry V.
• Is Part Of: European journal of inorganic chemistry. Issue 28(2016)
• Page Start: 4561
• Page End: 4564
• Publication Date: 2016-09-07
• Subjects: Palladium -- Carbene ligands -- Ligand oxygenation -- Atom transfer -- Oxygen; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201601019
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Stabilized with an N‐heterocyclic carbene ligand of the smallest steric profile, Pd II (η 2 ‐O2 )( I Me)2 ( I Me = 1, 3‐dimethylimidazole‐2‐ylidene) was synthesized by the direct addition of dioxygen to Pd 0 ( I Me)2 . The peroxidopalladium complex with I Me, which was previously available only by computation, was characterized by IR spectroscopy and X‐ray crystallography. Moreover, its oxygen‐atom‐transfer reactivity was elucidated by studying its thermolysis in pyridine at 60 °C to yield 1, 3‐dimethylimidazol‐2‐one ( I MeO) and its reaction with oxygen‐atom‐transfer acceptors such as PPh3 and (Me3 Si)2 . Abstract : Pd II (η 2 ‐O2 )( I Me)2 ( I Me = 1, 3‐dimethylimidazole‐2‐ylidene), which is used extensively in computational studies as a standard product of Pd 0 oxygenation, is synthesized and its oxygen‐atom transfer reactivity studied. Thermolysis of the complex leads to the formation of 1, 3‐dimethylimidazol‐2‐one ( I MeO), and its reaction with PPh3 and (Me3 Si)2 results in Ph3 PO and (Me3 Si)2 O, respectively.