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![The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)
The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding
Christian P Sindlinger1, Samuel R Lawrence2, Shravan Acharya3
1School of Chemistry, Monash University, 17 Rainforest Walk, Melbourne, Victoria 3800, Australia and Institut für Anorganische Chemie, Universität Göttingen, Tammannstr. 4, 37077 Göttingen, Germany.
Abstract:
The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L- = HC(Ph2P[double bond, length as m-dash]NDip)2-, Dip = 2,6-iPr2C6H3; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI24 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI25, prepared by iodination of LAlMe2, were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.
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