Mechanistic investigation of the Ru-catalyzed hydroamidation of terminal alkynes

The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis of enamides and enimides. Depending on the catalyst system employed, the reaction leads chemo-, regio-, and stereoselectively to a single diastereoisomer. Herein, we present a comprehensive mechanistic study of the ruthenium-catalyzed hydroamidation of terminal alkynes, which includes deuterium-labeling, in situ IR, in situ NMR, and in situ ESI-MS experiments complemented by computational studies. The results support the involvement of ruthenium-hydride and ruthenium-vinylidene species as the key intermediates. They are best explained by a reaction pathway that consists of an oxidative addition of the amide, followed by insertion of a π-coordinated alkyne into a ruthenium-hydride bond, rearrangement to a vinylidene species, nucleophilic attack of the amide, and finally reductive elimination of the product.     

A Reduced SNARE Model for Membrane Fusion

Let's get together : A minimal model system was developed to mimic the SNARE‐protein‐mediated fusion of biological membranes (see picture). Fusion between two populations of liposomes is controlled by a pair of complementary lipidated oligopeptides that form noncovalent coiled‐coil complexes and thereby force the membranes into close proximity to promote fusion. The model system displays the key characteristics of in vivo fusion events.

     

Stable étale realization and étale cobordism

We show that there is a stable homotopy theory of profinite spaces and use it for two main applications. On the one hand we construct an étale topological realization of the stable A¹-homotopy theory of smooth schemes over a base field of arbitrary characteristic in analogy to the complex realization functor for fields of characteristic zero.On the other hand we get a natural setting for étale cohomology theories. In particular, we define and discuss an étale topological cobordism theory for schemes. It is equipped with an Atiyah-Hirzebruch spectral sequence starting from étale cohomology. Finally, we construct maps from algebraic to étale cobordism and discuss algebraic cobordism with finite coefficients over an algebraically closed field after inverting a Bott element.     

Site connectivities in silver borophosphate glasses: new results from 11B{31P} and 31P{11B} rotational echo double resonance NMR spectroscopy

Local and medium range order in the glass system 50Ag2O-50[(B2O3)x-(P2O5)(1-x)] (x=0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6) have been investigated by high-resolution solid state nuclear magnetic resonance (NMR) techniques. The detailed local site distribution has been derived from deconvolution analysis of the 11B and 31P magic-angle spinning (MAS) NMR signals. Quantitative information regarding the extent of boron-oxygen-phosphorus connectivity has been obtained on the basis of 11B[31P} and 31P{11B} rotational echo double resonance experiments. Incorporation of borate into silver metaphosphate glasses produces four-coordinate BO4/2- sites, which crosslink the metaphosphate chains, resulting in a significant increase in the glass transition temperature. Furthermore, the presence of borate favors the disproportionation of P(2) chain-like units into P(1) and P(3) sites, an effect not observed in binary alkali phosphate glasses. Finally, borate incorporation beyond x=0.3 results in the formation of neutral BO3/2 units, indicating some net charge transfer from the borate to the phosphate network former species. This latter result corresponds to the general metal ion scavenging effect observed for phosphate species in other mixed network former glass systems. In the present system, the effect is relatively moderate, however, suggesting that anionic BO4/2- groups are stabilized by the interaction with the phosphate groups.     

Time-resolved infrared spectroscopic study of reactive acyl intermediates relevant to cobalt-catalyzed carbonylations

Time-resolved infrared spectroscopic studies have been used to characterize the reactive intermediate CH3C(O)Co(CO)2PPh3 (ICo), which is relevant to the mechanism of the catalysis of alkene hydroformylation by the phosphine-modified cobalt carbonyls. Step-scan FTIR and (variable) single-frequency time-resolved infrared detection on the microsecond time scale were used to record the spectrum of ICo and to demonstrate that the principal photoproduct of the subsequent reaction of this species at PCO = 1 atm is the methyl cobalt complex CH3Co(CO)3PPh3 (MCo). At higher PCO the trapping of ICo with CO to re-form CH3C(O)Co(CO)3PPh3 (ACo) (rate = kCO[CO][ICo]) was shown to become competitive with the rate of acetyl-to-cobalt methyl migration to give MCo (rate = kM[ICo]). Activation parameters for the competing pathways in benzene were determined to be delta H++CO = 57 +/- 04 kJ mol-1, delta S++CO = -91 +/- 12 J mol-1 K-1 and delta H++M = 40 +/- 2 kJ mol-1, delta S++M = -19 +/- 5 J mol-1 K-1. The effects of varying the solvent on the competitive reactions of ICo were also explored, and the mechanistic implications of these results are discussed.     

Versatile UHV system for combined far- and near-field magneto-optical microscopy of thin films

We have developed a UHV system for in situ studies of magnetic domains and magnetization reversal of thin films in the presence of external magnetic fields and at variable temperature. The system comprises a setup for magneto-optical Kerr effect measurements of magnetization curves, a Kerr-microscope for far-field magnetic-domain imaging, and a magneto-optical scanning near-field microscope in combination with a Sagnac interferometer (Sagnac-SNOM) for high-resolution imaging on a sub-μm scale. All components have successfully been tested, and the feasibility of studying ultrathin films has been demonstrated.     

Continuous group actions on profinite spaces

For a profinite group, we construct a model structure on profinite spaces and profinite spectra with a continuous action. This yields descent spectral sequences for the homotopy groups of homotopy fixed point spaces and for stable homotopy groups of homotopy orbit spaces. Our main example is the Galois action on profinite étale topological types of varieties over a field. One motivation is to understand Grothendieck’s section conjecture in terms of homotopy fixed points.     

From a Dy(III) Single Molecule Magnet (SMM) to a Ferromagnetic [Mn(II)Dy(III)Mn(II)] Trinuclear Complex

The Schiff base compound 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid (H(4)L) as a proligand was prepared in situ. This proligand has three potential coordination pockets which make it possible to accommodate from one to three metal ions allowing for the possible formation of mono-, di-, and trinuclear complexes. Reaction of in situ prepared H(4)L with Dy(NO(3))(3)·5H(2)O resulted in the formation of a mononuclear complex [Dy(H(3)L)(2)](NO(3))·(EtOH)·8(H(2)O) (1), which shows SMM behavior. In contrast, reaction of in situ prepared H(4)L with Mn(ClO(4))(2)·6H(2)O and Dy(NO(3))(3)·5H(2)O in the presence of a base resulted in a trinuclear mixed 3d-4f complex (NHEt(3))(2)[Dy{Mn(L)}(2)](ClO(4))·2(H(2)O) (2). At low temperatures, compound 2 is a weak ferromagnet. Thus, the SMM behavior of compound 1 can be switched off by incorporating two Mn(II) ions in close proximity either side of the Dy(III). This quenching behavior is ascribed to the presence of the weak ferromagnetic interactions between the Mn(II) and Dy(III) ions, which at T > 2 K act as a fluctuating field causing the reversal of magnetization on the dysprosium ion. Mass spectrometric ion signals related to compounds 1 and 2 were both detected in positive and negative ion modes via electrospray ionization mass spectrometry. Hydrogen/deuterium exchange (HDX) reactions with ND(3) were performed in a FT-ICR Penning-trap mass spectrometer.