Thionylimido Complexes

An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar₃Sb(NSO)₂), and copper examples [CuBipy(PPh₃)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding.     

Combined QCM-D/GE as a tool to characterize stimuli-responsive swelling of and protein adsorption on polymer brushes grafted onto 3D-nanostructures

A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties.     

Synthesis and Single Crystal Structures of N-Substituted Benzamides and Their Chemoselective Selenation/Reduction Derivatives

A series of N-aryl-N-(2-oxo-2-arylethyl) benzamides and cinnamides has been prepared. The reaction of the benzamides with Woollins’ reagent, a highly efficient chemoselective selenation/reduction reagent, gave the corresponding N-aryl-N-(arylenethyl) benzoselenoamides in good yields. Five representative single crystal X-ray structures are discussed.     

Synthesis and molecular structure of [CpRu(1,4,7-S3C6H12)]O3SCF3

The isolation and characterization of [CpRu(9S3)](O₃SCF₃), where 9S3 = 1,4,7-trithiacyclononane, is reported. The title compound crystallizes in the orthorhombic space group Pbca: a = 10.2542(18), b = 14.8991(13), c = 22.4832(18) Å, and Z = 8. The Ru atom is sandwiched between the -bound cyclopentadienyl ligand and the 9S3 ligand, bonding to all three of the sulfur atoms in the 9S3. The Ru—S distances are 2.2991(10), 2.2979(11), and 2.3055(10) Å. The C—S distances range from 1.819(4) to 1.852(5) Å in the trithiacyclononane ring.     

Anwendung des elektrostatischen Molekülmodells (RITTNER-Modells) auf Monohalogenide der Gruppen IIa,IIIa IVa und Ib

Newly calculated values of the dipol polarizabilities of singly charged metal ions are used in the calculation of the dissociation energy D₀ and of the anharmonicity constant ω_ex_e of group IIa, IIIa, IVa and Ib monohalides. Comparison with experimental values from literature suggests the empirical model as reasonable approximation.     

An unprecedented alpha-C-C agostic interaction in a cyclopropyl tris(pyrazolyl)boratoniobium complex

Structural, spectroscopic and theoretical evidence indicate that an unusual alpha-C-C agostic interaction is preferred over both alpha- and beta-C-H agostic alternatives in the title compound, TpMe2NbCl(c-C3H5)(MeCCMe).