Bis-Phosphaketenes LM(PCO)2 (M=Ga,In): A New Class of Reactive Group 13 Metal-Phosphorus Compounds |
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| Authors: | Dr Mahendra K Sharma Pratima Dhawan Dr Christoph Helling Dr Christoph Wölper Prof Dr Stephan Schulz |
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| Institution: | 1. Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5–7, 45141 Essen, Germany;2. Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5–7, 45141 Essen, Germany
These authors contributed equally to this work. |
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| Abstract: | Phosphaketenes are versatile reagents in organophosphorus chemistry. We herein report on the synthesis of novel bis-phosphaketenes, LM(PCO)2 (M=Ga 2 a , In 2 b ; L=HCC(Me)N(Ar)]2; Ar=2,6-i-Pr2C6H3) by salt metathesis reactions and their reactions with LGa to metallaphosphenes LGa(OCP)PML (M=Ga 3 a , In 3 b ). 3 b represents the first compound with significant In−P π-bonding contribution as was confirmed by DFT calculations. Compounds 3 a and 3 b selectively activate the N−H and O−H bonds of aniline and phenol at the Ga−P bond and both reactions proceed with a rearrangement of the phosphaethynolate group from Ga−OCP to M−PCO bonding. Compounds 2–5 are fully characterized by heteronuclear (1H, 13C{1H}, 31P{1H}) NMR and IR spectroscopy, elemental analysis, and single crystal X-ray diffraction (sc-XRD). |
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| Keywords: | bond activation double bonds gallium indium main-group elements phosphorus |
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