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Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: a Structurally Characterized Monomer–Dimer Pair For Gallium
Umeå University, Faculty of Science and Technology, Department of Chemistry. School of Chemistry, Melbourne, Australia).ORCID iD: 0000-0002-3804-6421
2017 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 23, no 2, 447-455 p.Article in journal (Refereed) Published
Abstract [en]

We have synthesized and characterized the monomeric diiminophosphinate-stabilized Group 13 metal(I) complexes [DipLE:], DipL=Ph2P(NDip)2, Dip=2,6-iPr2C6H3; E=Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL=Ph2P(NMes)2, Mes=2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E=Al−Tl, shed light on the bonding in these compounds and show that the newly formed E−E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E=Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

Place, publisher, year, edition, pages
2017. Vol. 23, no 2, 447-455 p.
Keyword [en]
Group 13 elements, low valent main group compounds, metal–metal interactions, N-ligands, O–O activation
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-130166DOI: 10.1002/chem.201604495ISI: 000393618700032PubMedID: 27813169OAI: oai:DiVA.org:umu-130166DiVA: diva2:1064795
Available from: 2017-01-13 Created: 2017-01-13 Last updated: 2017-08-14Bibliographically approved

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CiteExportLink to record
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Citation style
  • apa
  • harvard1
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