| 1. |
- Hawley, Andrew L., et al.
(författare)
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Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates : a Structurally Characterized Monomer–Dimer Pair For Gallium
- 2017
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 23:2, s. 447-455
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 2. |
- Lawrence, Samuel R., et al.
(författare)
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Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium
- 2019
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 10:46, s. 10755-10764
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Tidskriftsartikel (refereegranskat)abstract
- The reaction of the magnesium(i) complexes [{((Ar)nacnac)Mg}(2)], ((Ar)nacnac = HC(MeCNAr)(2), Ar = Dip (2,6-iPr(2)C(6)H(3)), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C-60 afforded a series of hydrocarbon-soluble fulleride complexes [{((Ar)nacnac)Mg}(n)C-60], predominantly with n = 6, 4 and 2. C-13{H-1} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{((Ar)nacnac)Mg}(n)C-60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [((Ar)nacnac)Mg](+) ions with C-60(n-) anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C-60(6-) ion. Experimental studies show the flexible ionic nature of the {((Ar)nacnac)Mg}+MIDLINE HORIZONTAL ELLIPSISC606- coordination bonds. DFT calculations on the model complex [{((Me)nacnac)Mg}(6)C-60] ((Me)nacnac = HC(MeCNMe)(2)) support the formulation as an ionic complex with a central C-60(6-) anion and comparable frontier orbitals to C-60(6-) with a small HOMO-LUMO gap. The reduction of C-60 to its hexaanion gives an indication about the reducing strength of dimagnesium(i) complexes.
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| 3. |
- Sindlinger, Christian P., et al.
(författare)
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PNacPNacE : (E = Ga, In, Tl) - monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide
- 2017
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 46:48, s. 16872-16877
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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