Selective Manipulation of Well-Defined Trinuclear Pd(II)-Complexes.

Several strategies are available to design well-defined multimetallic molecular entities bearing functional ligands. Substoichiometric exchange reactions in the coordination sphere of pre-existing multinuclear precursors are relatively underexploited in this context. Palladium(II) acetate is not a mononuclear compound in the solid state but rather exists as a trimer, i.

PhenTAA: A Redox-Active N-Macrocyclic Ligand Featuring Donor and Acceptor Moieties.

Here, we present the development and characterization of the novel PhenTAA macrocycle as well as a series of [Ni(RPhenTAA)] complexes featuring two sites for ligand-centered redox-activity. These differ in the substituent R (R = H, Me, or Ph) and overall charge of the complex n (n = -2, -1, 0, +1, or +2). Electrochemical and spectroscopic techniques (CV, UV/vis-SEC, X-band EPR) reveal that all redox events of the [Ni(RPhenTAA)] complexes are ligand-based, with accessible ligand charges of -2, -1, 0, +1, and +2.

Geometrically Deformed and Conformationally Rigid Phosphorus Trisamides Featuring an Unsymmetrical Backbone.

Nonclassical P(III) centers have attracted much attention in recent years. Incorporating a P(III) center in a rigid bicyclic platform offers a particularly attractive way to invoke significant geometric distortion of the phosphorus atom that may in turn induce unusual reactivity. Although still relatively scarcely explored, phosphorus centers enforced in a non-C symmetry have gained significant traction lately.

Probing the influence of substrate binding on photocatalytic dehalogenation with a heteroleptic supramolecular [MLL] square containing PDI photosensitizers as ligands.

Photoredox catalysis is a valuable tool in a large variety of chemical reactions. Main challenges still to be overcome are photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. A potential solution to these challenges is the pre-organization of the photosensitizer, substrate and (co)-catalyst in supramolecular self-assembled structures.

Reactivity of a Unique Si(I)-Si(I)-Based η-Bis(silylene) Iron Complex.

In this paper, we report the synthesis of a unique silicon(I)-based metalla-disilirane and report on its reactivity toward TMS-azide and benzophenone. Metal complexes containing disilylenes ((bis)silylenes with a Si-Si bond) are known, but direct ligation of the Si(I) centers to transition metals always generated dinuclear species. To overcome this problem, we targeted the formation of a mononuclear iron(0)-silicon(I)-based disilylene complex via templated synthesis, starting with ligation of two Si(II) centers to iron(II), followed by a two-step reduction.