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In a recent collaborative paper with several groups of the SFB 3MET we reported on a detailed theoretical and spectroscopic study on the electronically excited states of a highly symmetric, trinuclear palladium complex both in the gas phase and in solution. The results were published in Phys. Chem. Chem. Phys. (click here)





The preparation and structures of coinage metal complexes of tris(pyrazolyl)methanide-based redox-active metalloligands are reported, together with density functional theory (DFT) calculations and detailed cyclic voltammetry studies in solution in order to elucidate a conceivable electronic interplay between the metal atoms. The results were recently published in Organometallics (click here)





Recently, the 5th German edition of the renowned Inorganic Chemistry textbook “Huheey” appeared, again with contributions from our side.

Huheey, James E. / Keiter, Ellen A. / Keiter, Richard L.

Anorganische Chemie

Hrsg. v. Steudel, Ralf

Bearb. v. Breher, Frank / Finze, Maik / Johrendt, Dirk / Lunk, Hans-Joachim / Kaupp, Martin / Radius, Udo / Schatzschneider, Ulrich
DeGruyter, 2014





 

By using a multifunctional silyl ligand based on the tris(3,5-dimethylpyrazolyl)silyl scaffold [Si(3,5-Me2pz)3], we succeeded in obtaining the homoleptic tetrakis(silyl) complexes of Pd0 and Pt0, which were characterized by various methods, including multinuclear NMR spectroscopic techniques, cyclic voltammetry in combination with DFT calculations, X-ray crystallography, and EPR spectroscopy. The complexes form very unusual metal-centered heterocubane structures in the solid state and in solution. The rather rigid heterocubane ligand shells were found to facilitate the stepwise, quasi-reversible oxidation to their d9 MI and d8 MII analogues (click here; see also cover of issue 52 and spotlight on ChemistryViews).




 

The preparation and structure of the first metallacyclic alkyl-amido carbene complex is reported, including NMR spectroscopic, computational and cyclic voltammetry studies of the bimetallic RuII-IrIII complex. The results were recently published in Dalton Trans. (special issue).




 

Season‘s Greetings from the group (click here; by Timo Augenstein)

 


 

In a recent collaborative study we reported on the development of a metal ion-mediated base pair for electron transfer in DNA (Chem. Eur. J.; click here). A new C-nucleoside that is structurally based on the hydroxyquinoline ligand, which is able to form stable pairs in DNA both in the absence and in the presence of metal ions, was synthesized in the group of H.-A. Wagenknecht (KIT). Subsequently, our group has probed the interactions between the metal centers in adjacent CuII-mediated base pairs in DNA by electron paramagnetic resonance (EPR) spectroscopy. The metal-metal distance falls into the range of previously reported values.



 

The preparation and structures of organochalcogenyl-substituted bicyclo[1.1.1]pentanes of Group 14 have been reported, together with detailed NMR spectroscopic studies in solution. (click here)



 

Heterobimetallic Cuprates: Several bimetallic silyl halido cuprates of the general formula [CuX{Si(3,5-Me2pz)3Mo(CO)3}]- are reported in a recent
Full Paper in Chemistry. (click here) The electronic and structural properties of the complexes were probed in detail by X-ray diffraction analysis, IR-induced multiphoton dissociation studies, cyclic voltammetry, gasphase photoelectron spectroscopy, UV/Vis and fluorescence spectroscopy. The frontispiece in issue 26 shows a van der Waals plot of the silyl chloro cuprate in the background and the different characterization techniques applied in the foreground.




Several rare earth coordination compounds and the first actinide coordination compound of a multifunctional ligand have been synthesized and characterized in detail in the solid state and in solution by various methods. Pulsed field-gradient spin-echo (PGSE) diffusion measurements and 1H,19F heteronuclear Overhauser spectroscopy (HOESY) revealed that, in particular, the Pu(III) complex shows a strong tendency to form solvent-separated ion pairs in acetonitrile solution. The results were recently published in Chemical Science (click here)





Group 14-element-bridged [1]-, [2]-, and [3]chromoarenophanes were studied by EPR and UV/Vis spectroscopy, as well as electrochemical and computational methods. The unpaired electron mainly occupies a dz2 orbital on Cr, irrespective of the size of the ansa bridge. Unselective insertion of a platinum(0) fragment into a C-Sn bond was found in a stanna[1]chromoarenophane, thereby giving rise to a heterobimetallic complex. This paper was produced in collaboration with the Braunschweig group (Würzburg) and selected as Very Important Paper (VIP).




2D 7Li,15N heteronuclear shift correlation has been applied to several lithiumorganyls consisting of polydentate N ligands such as
TMEDA, PMDTA and (-)-sparteine. In combination with other spectroscopic techniques, details on the formation of the lithiumorganyl polyamine adducts, as well as the strength of ion pairing in solution has been explored (collaboration with the Fernández group, Almeria; click here).


 




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