A combined experimental and quantum chemical study on thallium(I) tris(pyrazolyl)methanide. (29th March 2017)

• Record Type: Journal Article
• Authors: Kuzu, Istemi; Baldes, Alexander; Weigend, Florian; Breher, Frank
• Is Part Of: Polyhedron. Volume 125(2017)
• Page Start: 74
• Page End: 79
• Publication Date: 2017-03-29
• Subjects: Tripodal ligands -- Poly(pyrazolyl) ligands -- Tris(pyrazolyl)methanide -- Thallium -- N-donor ligands; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.09.017
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: A combined experimental and quantum chemical study on thallium(I) tris(pyrazolyl)methanide is provided. An X-ray diffraction study revealed that complex consists of a κ 2 N, κ 1 C coordination mode of the tris(pyrazolyl)methanide ligand. The results were supported by DFT calculations. Abstract: Density functional theory methods have been applied to identify the favoured structural motif of thallium(I) tris(pyrazolyl)methanide complexes. The reaction of [TlN(SiMe3 )2 ]2 with tris(pyrazolyl)methane HC(pz)3 (with pz = pyrazolyl) in toluene furnished the highly air-sensitive title compound [Tl( H Tpmd)] (4 ) (with H Tpmd = [C(pz)3 ] − ). An X-ray diffraction study revealed that complex4 consists of a single bond between the thallium(I) cation and the carbanion of H Tpmd ligand entity. This Tl–C bond (254.1(8) pm) is supported by two additional Tl⋯N contacts (Tl⋯N: 273.6(7) and 293.1 pm) provided by the N donor atoms of two pyrazolyl scaffolds of the tripodal ligand. Overall, a κ 2 N, κ 1 C coordination mode of the tris(pyrazolyl)methanide ligand is at hand in complex4 . Furthermore, the title compound forms a weak dimer in the solid-state by additional intermolecular Tl⋯N′ interactions (318.7 pm).