title: Synthesis and comparison of transition metal complexes of abnormal and normal tetrazolylidenes: a neglected ligand species.
abstract: To date, only few examples of tetrazolylidene carbenes coordinated to transition metal complexes have been described. A direct comparison of "normal" tetrazolylidenes (1,4-substitution pattern) and "abnormal" tetrazolylidenes (also referred to as "mesoionic carbenes"; 1,3-substitution pattern) has not been performed at all. In this work, we describe coordination of both ligand types to a row of transition metals. For example, the first examples of tetrazolylidene Mo, Ag, or Ir complexes have been isolated and fully characterized. The mesoionic tetrazolylidene Ag compound 2d is shown to be a viable carbene transfer reagent. By means of NMR, IR, and Raman spectroscopy, as well as X-ray crystallography and computational results, the pronounced differences between the two ligand substitution patterns are highlighted. It is shown that simply changing the position of a methyl group from N3 to N4 in the heterocycle can cause enormous differences in ligand characteristics.
authors.affiliation: Catalysis Research Center, Technische Universität München, Ernst-Otto-Fischer-Str. 1, D-85747 Garching bei München, Germany.
authors.forename: Lars-Arne
authors.initials: LA
authors.lastname: Schaper
authors.forename: Xuhui
authors.initials: X
authors.lastname: Wei
authors.forename: Philipp J
authors.initials: PJ
authors.lastname: Altmann
authors.forename: Karl
authors.initials: K
authors.lastname: Öfele
authors.forename: Alexander
authors.initials: A
authors.lastname: Pöthig
authors.forename: Markus
authors.initials: M
authors.lastname: Drees
authors.forename: János
authors.initials: J
authors.lastname: Mink
authors.forename: Eberhardt
authors.initials: E
authors.lastname: Herdtweck
authors.forename: Bettina
authors.initials: B
authors.lastname: Bechlars
authors.forename: Wolfgang A
authors.initials: WA
authors.lastname: Herrmann
authors.forename: Fritz E
authors.initials: FE
authors.lastname: Kühn
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D013777:Tetrazoles / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D013777:Tetrazoles; D028561:Transition Elements