Browsing by Author "Schmidbaur, Hubert"

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    18-Membered heterometallacyclic gold(I) compounds : structural influences of co-crystallized solvent
    (De Gruyter, 2012-08) Dobrzanska, Liliana; Strasser, Crishtoph E.; Schmidbaur, Hubert; Raubenheimer, Helgard G.
    ABSTRACT: No abstract available.
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    Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions
    (Wiley, 2020-02) Schmidbaur, Hubert; Raubenheimer, Helgard G.
    Excimers and exciplexes are defined as assemblies of atoms or molecules A/A’ where interatomic/intermolecular bonding appears only in excited states such as [A2]* (for excimers) and [AA’]* (for exciplexes). Their formation has become widely known because of their role in gas-phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration AuI (5d10)) through aurophilic contacts. In the corresponding excimers, a new type of Au···Au bonding arises, with bond energies and lengths approaching those of ground-state Au@Au bonds between metal atoms in the Au0 (5d106s1) and AuII(5d9) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.
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    Gold coordination during homogeneous alkyne and allene cyclisation catalysis : coordination to substrates, to ancillary ligands and in intermediates
    (AOSIS Publishing, 2011-03-16) Raubenheimer, Helgard G.; Schmidbaur, Hubert
    The ever-increasing role of homogeneous gold catalysis in organic synthesis and the consequent need to be able to rationally control the rate and outcome of such reactions has emphasised the importance of each successive metal–carbon coordination step. Concentrating on alkyne and allene cyclisation and upon reaction mechanisms postulated on the basis of empirical and theoretical results, we have examined the coordination of gold fragments to triple bonds, the modification of gold(I) precatalysts to effect specific reaction pathways or enantioselectivity and the isolation of coordinated intermediates or model compounds thereof. Some of the recent advances that have been made in various laboratories are described in this compact review.