Novel tosyl- and mesitylsulfonyl-substituted triazaphospholes were synthesized and structurally characterized. In an attempt to prepare the corresponding Au(i)-complexes with stoichiometric amounts ...of AuCl·S(CH3)2, cyclo-1,3-diphospha(iii)-2,4-diazane-AuCl-complexes were obtained instead. Our here presented results offer a new strategy for preparing such coordination compounds selectively in a one-pot approach.
Transient absorption data of FeII(tpy)(CN)3− reveals spectroscopic signatures indicative of 3MLCT with a ∼10 ps kinetic component. These data are supported by DFT and TD-DFT calculations, which show ...that excited state ordering is responsive to the number of cyanide ligands on the complex.
Unlike Ru2(μ-O2CCH3)4, the structurally analogous water-soluble Ru2II,III diphosphonato complex K3Ru2(hedp)2(H2O)2 (K3·1) is only involved in stoichiometric water oxidation with a maximum 67% O2 ...yield under CAN/HNO3 solution (pH 1.0) for 2.5 h. The water oxidation mechanism and intermediate products were ascertained by UV-vis, ESI-MS and DFT calculation.
Semantics, definitions? The description of the electronic structure of main‐group compounds with dative bonds significantly enriched the chemistry of sp block elements. The new viewpoint has proved ...to be a useful guideline for the synthesis of unusual donor–acceptor complexes and for explaining novel molecular structures. New compound classes such as carbones CL2 and borylene complexes (BH)L2 have been found.
Harnessing visible light to access excited (triplet) states of organic compounds can enable impressive reactivity modes. This tutorial review covers the photophysical fundamentals and most ...significant advances in the field of visible-light-mediated energy transfer catalysis within the last decade. Methods to determine excited triplet state energies and to characterize the underlying Dexter energy transfer are discussed. Synthetic applications of this field, divided into four main categories (cyclization reactions, double bond isomerizations, bond dissociations and sensitization of metal complexes), are also examined.
Risky business? The use of dative bonds to describe the electronic structure of main‐group compounds has come into vogue in recent years. But where are the limits? When does the description as a ...dative bond make sense and when is this view misleading? This Essay develops the idea on the basis of current examples.
Photoredox chemistry with organic or transition metal agents has been reviewed in earlier years, but such is the pace of progress that we will overlap very little with earlier comprehensive reviews. ...This review first presents an overview of the area of research and then examines recent examples of C-C, C-N, C-O and C-S bond formations
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radical intermediates with transition metal and organic radical promoters. Recent successes with Birch reductions are also included. The transition metal chemistry will be restricted to photocatalysts based on the most widely used metals, Ru and Ir, but includes coupling chemistries that take advantage of low-valent nickel, or occasionally copper, complexes to process the radicals that are formed. Our focus is on developments in the past 10 years (2011-2021). This period has also seen great advances in the chemistry of organic photoredox reagents and the review covers this area. The review is intended to present highlights and is not comprehensive.
Visible light-activated reactions continue to expand and diversify. The example shown here is a Birch reduction achieved by organophotoredox reagents.