Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates : a Structurally Characterized Monomer–Dimer Pair For Gallium

• 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.

Subject headings

NATURVETENSKAP  -- Kemi -- Oorganisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)

Keyword

Group 13 elements

low valent main group compounds

metal–metal interactions

N-ligands

O–O activation

Publication and Content Type

ref (subject category)

art (subject category)