From a nanoparticular solid-state material to molecular organo-f-element-polyarsenides.

A convenient pathway to new molecular organo-lanthanide-polyarsenides in general and to a f-element complex with the largest polyarsenide ligand in detail is reported. For this purpose, the activation of the solid state material As (nanoscale gray arsenic) by the multi electron reducing agents [K(18-crown-6)][(Ln)(μ-η:η-CH)] (Ln = La, Ce, Cp'' = 1,3-bis(trimethylsilyl)cyclopentadienyl anion) and [K(18-crown-6)][(Ln)(μ-η:η-CH)] (Ln = Ce, Nd) is shown. These non-classical divalent lanthanide compounds were used as three and four electron reducing agents where the product formation can be directed by variation of the applied reactant.

Investigation of the Coordination Chemistry of a Bisamidinate Ferrocene Ligand with Cu, Ag, and Au.

The coordination chemistry of a ferrocene ligand with one bulky amidinate function attached to each ring toward two different coinage metal precursors was investigated. In dependence of the metal and the co-ligands, "ansa" type structures and non-bridged structures were obtained. Six different compounds are reported.

Hetero-bimetallic Lanthanide-Coinage Metal Compounds Featuring Possible Metal-Metal Interactions in the Excited State.

Heterometallic complexes, combining metals of the outer rims of the d-block, for example lanthanides(III) (Ln) and coinage metals(I) (M) are scarcely reported, synthetically challenging and highly interesting in terms of their interactions. In this context, we synthesized hetero-bimetallic Ln-M compounds ligated by the phosphine functionalized amidinate system (N,N'-bis[(2-diphenylphosphino)phenyl]formamidinate, "dpfam"). The resulting compounds [dpfam LnM][OTf] (Ln = La, Nd and M = Ag, Au) feature a close proximity of the two metal centres and were investigated experimentally by photoluminescence spectroscopy and quantum chemical calculations.

d/f-Polypnictides Derived by Non-Classical Ln Compounds: Synthesis, Small Molecule Activation and Optical Properties.

Reduction chemistry induced by divalent lanthanides has been primarily focused on samarium so far. In light of the rich physical properties of the lanthanides, this limitation to one element is a drawback. Since molecular divalent compounds of almost all lanthanides have been available for some time, we used one known and two new non-classical reducing agents of the early lanthanides to establish a sophisticated reduction chemistry.

Synthesis of Unprecedented 4d/4f-Polypnictogens.

A series of 4d/4f-polyarsenides, -polyarsines and -polystibines was obtained by reduction of the Mo-pnictide precursor complexes [{Cp Mo(CO) } (μ,η -E )] (E=As, Sb; Cp =tBu substituted cyclopentadienyl) with two different divalent samarocenes [Cp* Sm] and [(Cp ) Sm]. For the reductive conversion of the Mo-stibide only one product was isolated, featuring a planar tetrastibacyclobutadiene moiety as an unprecedented ligand for organometallic compounds. For the corresponding Mo-arsenide a tetraarsacyclobutadiene and a second species with a side-on coordinated As anion was isolated.

Dimolybdenum Paddlewheel as Scaffold for Heteromultimetallic Complexes: Synthesis and Photophysical Properties.

A diphenylphosphine functionalized benzoic acid was applied for the synthesis of a homoleptic dimolybdenum-based metalloligand, exhibiting four symmetrically placed phosphine donor sites. This allowed subsequent treatment with gold(I), rhodium(I), and iridium(I) precursors to obtain early-late heterometallic complexes as well as Lewis acid-base adducts with BH. The compounds were in-depth investigated by spectroscopic techniques, single-crystal X-ray diffraction, and femtosecond laser spectroscopy.