Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates : a structurally characterized monomer-dimer pair for gallium
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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.
Hawley , A L , Ohlin , C A , Fohlmeister , L & Stasch , A 2017 , ' Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates : a structurally characterized monomer-dimer pair for gallium ' Chemistry - A European Journal , vol 23 , no. 2 , pp. 447-455 . DOI: 10.1002/chem.201604495
Chemistry - A European Journal
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/chem.201604495
A. S. is grateful to the Australian Research Council for support and a fellowship. C. A. O. thanks the Australian Research Council for Discovery Project grants DP11015530 and DP130100483.
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