The first liquid-phase synthesis of high-quality, small-sized rare-earth metal nanoparticles (1-3 nm)-ranging from lanthanum as one of the largest (187 pm) to scandium as the smallest (161 pm) rare-earth metal-is shown. Size, oxidation state, and reactivity of the nanoparticles are examined (e.g., electron microscopy, electron spectroscopy, X-ray absorption spectroscopy, selected reactions). Whereas the nanoparticles are highly reactive (e.g. in contact to air and water), they are chemically stable as THF suspensions and powders under inert conditions. The reactivity can be controlled to obtain inorganic and metal-organic compounds at room temperature.

In this work we detail our efforts to systematically generate stable dicoordinate Cu II complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf (1). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X = monoanionic ligand) proved difficult as many of the complexes rapidly decomposed in solution. By using triflate-related ligands such as ethyl sulfate and bistriflimide, the additional dicoordinate copper complexes RCuOSO 3 Et (2), [RCu(THF)][Cu(NTf 2 ) 2 ] (3) and RCuNTf 2 (4) could be isolated. Spectroscopic indications corroborate more Cu I than Cu II character in all RCuX derivatives.

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The sterically demanding 1,8-bis(3,5-ditertbutylphenyl)-3,6-di-tert-butylcarbazole (dtbpCbz)–H was deprotonated with various metal bases to obtain a complete series of thermally robust alkali metal compounds of the type [(dtbpCbz)M] (M = Li, Na,...

Dedicated to Prof. Cameron Jones on the occasion of his 60 th birthday.In this contribution, the synthesis and properties of nine novel 3d metal complexes are reported. As supporting ligand scaffold, the bulky 1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazole (R) was employed. After deprotonation and salt metathesis reactions, a series of four complexes, the dimeric [RMn(THF)(μ-Cl)] 2 (1 a), [RFe(THF)(μ-Cl)] 2 (2 a), and [RCo(THF)(μ-Cl)] 2 (3 a) as well as a monomeric [RCr(THF) 2 (Cl)] (4 a), were obtained, while the analogous Ni(II) complex remained elusive. However, incorporation of PMe 3 as stronger donor molecule in comparison sufficed to stabilise also the Ni(II) complex [RNi(PMe 3 ) 2 (Cl)] (5 b). The series was completed by treatment of 1 a-4 a with PMe 3 , which afforded the related phosphine complexes 1 b-4 b. All complexes were characterised in the solid state by single crystal structure elucidation and their magnetic moments in solution were determined by NMR experiments with the Evans method.