Neutral and cationic Metallaphosphenes of Group 13 - Synthesis, Structure and Reactivity

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Group 13/15 compounds of the heavier elements with π-bonding contribution are still a scientific task. While B–N and Al–N compounds have been synthesized and their interesting chemical reactivity has been shown in recent years, analogous compounds of the heavier elements are still rare. In this research project we want to develop a general route for the synthesis of neutral homo- and heterobimetallic metallaphosphenes L(X)MPM'L (M, M' = Al, Ga In) with π-bonding contribution as well as the corresponding cationic species [LMPML]+. The promising high reactivity of the M–P double bond, which was demonstrated in preliminary studies, will be used for bond activation reactions of small molecules. In these reactions, we will also evaluate the influence of the polarity of the M–P double bond (M = Al, Ga, In) on the reactivity / selectivity. Aside from stoichiometric bond activation reactions, we will also try or the first time to use metallaphosphenes for catalytic reactions using selected substrates. Finally, we want to use di- and trisubstituted metallaphosphaketenes (LM(PCO)2, M(PCO)3) for the synthesis of so far unknown di- and trimetallaphosphenes (LM(PML1)2, M(PML1)3), which may show interesting cooperative effects in bond activation reactions. Quantum chemical calculations as well as in situ 1H and 31P NMR spectroscopic studies will be performed to get deeper insights into the electronic structure of the compounds as well as to identify possible reaction mechanism.