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PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide

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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 LGaI2 4 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 LAlI2 5, 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.

Graphical abstract: PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide

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Publication details

The article was received on 27 Oct 2017, accepted on 23 Nov 2017 and first published on 23 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT04048B
Citation: Dalton Trans., 2017, Advance Article
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    PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide

    C. P. Sindlinger, S. R. Lawrence, S. Acharya, C. A. Ohlin and A. Stasch, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT04048B

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