title: A singlet biradicaloid zinc compound and its nonradical counterpart.
abstract: Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077 Göttingen, Germany.
authors.forename: Amit Pratap
authors.initials: AP
authors.lastname: Singh
authors.forename: Prinson P
authors.initials: PP
authors.lastname: Samuel
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky
authors.forename: Martin C
authors.initials: MC
authors.lastname: Schwarzer
authors.forename: Gernot
authors.initials: G
authors.lastname: Frenking
authors.forename: Navdeep S
authors.initials: NS
authors.lastname: Sidhu
authors.forename: Birger
authors.initials: B
authors.lastname: Dittrich
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002712:Chlorides / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004148:Dioxolanes / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D011789:Quantum Theory; D017967:Zinc Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D000480:Alkynes; D002712:Chlorides; D004148:Dioxolanes; D017967:Zinc Compounds; C504703:aminocarbene; C016837:zinc chloride