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 usingMesL=Ph2P(NMes)2, Mes=2,4,6-Me3C6H2afforded 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.
School of Chemistry, Monash University, 17 Rainforest Walk, Melbourne, Victoria, 3800, Australia.
Andrew L
AL
Hawley
School of Chemistry, Monash University, 17 Rainforest Walk, Melbourne, Victoria, 3800, Australia.|Department of Chemistry, Umeå University, Linnaeus väg 10, Umeå, 907 36, Sweden.
C André
0000-0002-3804-6421
CA
Ohlin
School of Chemistry, Monash University, 17 Rainforest Walk, Melbourne, Victoria, 3800, Australia.
Lea
L
Fohlmeister
School of Chemistry, Monash University, 17 Rainforest Walk, Melbourne, Victoria, 3800, Australia.|EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, UK.
Andreas
0000-0002-7407-8287
A
Stasch
Group 13 elements; N-ligands; O-O activation; low valent main group compounds; metal-metal interactions