Activation of Molecular Hydrogen by a Singlet Carbene through Quantum Mechanical Tunneling1. (17th February 2015)

• Record Type: Journal Article
• Authors: Henkel, Stefan; Sander, Wolfram
• Is Part Of: Angewandte Chemie. Volume 127:Number 15(2015)
• Page Start: 4686
• Page End: 4690
• Publication Date: 2015-02-17
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201410501
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Carbenes are among the few metal‐free molecules that are able to activate molecular hydrogen. Whereas triplet carbenes have been shown to insert into H₂ through a two‐step mechanism that at low temperature is assisted by quantum mechanical tunneling (QMT), singlet carbenes insert in concerted reactions with considerable activation barriers, and are thus unreactive towards H₂ at cryogenic temperatures. Here we show that 1‐azulenylcarbene with a singlet ground state readily inserts into H₂, and that QMT governs the insertion into both H₂ and D₂. This is the first example that shows that QMT can also be important for singlet carbenes inserting into dihydrogen.</p> </abstract>