title: Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex.
abstract: Actinide complexes demonstrate unparalleled reactivity towards small molecules. However, utilizing these powerful transformations in a predictable and deliberate manner remains challenging. Therefore, developing actinide systems that not only perform noteworthy chemistry but also demonstrate controllable reactivity is a key goal. We describe a bis(NHC)borate thorium-bpy complex (1) that is capable of reductively cleaving the R-NC bond in a series of organic isocyanides. In contrast to most actinide-mediated bond activations, the dealkylation event mediated by 1 is remarkably general and yields very well-defined products that assist in mechanistic elucidation. Synthesis of the rearranged but-3-enyl product from the reaction of 1 and cyclopropylmethyl isocyanide supports the notion of a radical-based mechanism.
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
authors.forename: Mary E
authors.identifier: 0000-0002-4630-0661
authors.initials: ME
authors.lastname: Garner
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
authors.forename: Stephan
authors.identifier: 0000-0002-5353-0801
authors.initials: S
authors.lastname: Hohloch
authors.affiliation: LPCNO, Université de Toulouse, 135 Avenue de Rangueil, 31077, Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.affiliation: Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA. arnold@berkeley.edu.
authors.forename: John
authors.identifier: 0000-0001-9671-227X
authors.initials: J
authors.lastname: Arnold
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013910:Thorium / Q000737:chemistry*
chemical_list: D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; C030011:carbene; D015082:2,2'-Dipyridyl; D013910:Thorium; D002244:Carbon; D009584:Nitrogen; D008697:Methane
keywords: N-heterocyclic carbenes; bipyridine; cooperativity; isocyanide; thorium