From new transition metal carbonyl and nitrosyl cations of the 5th to 10th group to 'naked' M+ synthons and their use for substitution reactions, activation of small molecules and access to potential catalysts

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With this prolongation proposal we describe routes to prepare novel elusive homoleptic transition metal carbonyl or nitrosyl cations, but also the first steps towards homoleptic dinitrogen cations. We use them for further substitution chemistry targeting organometallic textbook additions as well as potential catalyst cations suitable for small molecule activation, the latter using the earth-abundant metals Cr…Ni, with a focus on Fe and Co. For this chemistry, one needs suitable and weakly coordinating (counter)anions (WCAs) as well as suitable oxidants, or more correctly, deelectronators for the ionization of the neutral precursors. In the first period we have established access to almost ideal WCAs as well as novel deelectronators in innovative solvent systems like ortho-difluorobenzene or 1,2,3,4-tetrafluorobenzene. The full potential of these methodologies shall be explored with this second funding period to prepare a wealth of textbook compounds of basic importance for the chemistry of the elements. The methods and materials shall be lifted to a generally applicable level for wide use in the synthetic chemistry community.Last, but not least we will continue to develop the concept of traceless transfer oxidation.