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PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide
Umeå University, Faculty of Science and Technology, Department of Chemistry.
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2017 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 46, no 48, p. 16872-16877Article in journal (Refereed) Published
Abstract [en]

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L-=HC(Ph(2)PvNDip)(2)(-), Dip=2,6-(Pr2C6H3)-Pr-i; 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.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2017. Vol. 46, no 48, p. 16872-16877
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Inorganic Chemistry
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URN: urn:nbn:se:umu:diva-143502DOI: 10.1039/c7dt04048bISI: 000417846200018PubMedID: 29188251OAI: oai:DiVA.org:umu-143502DiVA, id: diva2:1170513
Available from: 2018-01-03 Created: 2018-01-03 Last updated: 2018-06-09Bibliographically approved

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Ohlin, C. André

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