Stereochemische untersuchungen an C-10-disubstituierten C-9-hydroxyphäophorbiden der a-reihe

The diastereomeric 9-hydroxy pheophorbides 3a, b-1, 2 and 4a, b-1, 2 were prepared by reduction of the 10-alkoxy pheophorbides 1a, b and 2a, b with NaBH₄. Their absolute configuration at C-10 was determined by NMR- and ORD/CD-measurements as well as chemical correlation, the configuration at C-9 by IR- and mainly NMR-spectroscopy. For this purpose, the NMR-spectra of the 9-hydroxy pheophorbides 3a, b-1, 2 had completely to be assigned with the aid of the selectively deuterated alcohols 5a, b-1, 2. The configuration at C-10 is stable under the conditions of the alkaline reduction while C-9 partially epimerizes. The acidic alcoholysis of 3a, b-1, 2, however, proceeds by equilibration at C-10 and almost complete retention at C-9. The H-bonds between the 9-OH group and the C-10 substituents (-COOCH₃, -OCH₃ were investigated by NMR and IR spectroscopy.     

A π-acceptor series for phosphines from51V N.M.R. data on [η5-CpV(CO)3L] complexes

Summary Qualitative molecular orbital considerations of the complexes [⁵-CPV(CO)₃ L] (L = substituted phosphane, SbPh₃, AsPh₃, CN^–) suggest that s' V chemical shift parameters () obtained for these compounds should correlate with the -acceptor abilities of L. Based on observed r-values, the ligands are arranged in sequence of their -acceptor ability, which lies in the order P(OR)₃ > CN^– > PR'₃3 SbPh₃ PPhF₂ > P(i-Bu)₃ P(NR ₂ )₃ > PPh₃ > AsPh₃ Nuclear spin-spin coupling constants J (⁵¹V-³¹ P), line widths H and i.r. data in the (CO) region are also presented.P(OR)₃ = P(OEt)₃, 4-Ethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]-octane; R = Me, n-Pr; R = Me, Et.     

Eine Notiz zum A-Typ der Lanthanoidoxide: Über Pr2O3

The A-type of Lanthanoide Oxides: On Pr₂O₃ . “Reductive” thermal decomposition of K₂PrO₃ [Ni-cylinder, semi-open system, 1000°C, 14 d] leads for the first time to light green single crystals of Pr₂O₃. The structure determination [105 symmetry independent hkl, four circle diffractometer Philips PW 1100; MoKα; R = 6.30%, R_w = 5.01%; space group P3m1; Z = 1; a = 385.77(3), c = 601.20(6) pm] verifies the A-type according to the proposed structure by PAULING .     

The electrical properties of semiconductor/metal,semiconductor/liquid,and semiconductor/conducting polymer contacts

Critical comparisons are drawn between the basic electrical properties of semiconductor/metal, semiconductor/liquid, and semiconductor/conducting polymer junctions. A theoretical model is developed to describe the basic current-voltage properties of semiconductor contacts, with emphasis on the contrasts between ideal and observed behavior. Using the concepts from this model, the characteristics of a variety of semiconductor contacts are evaluated. The discussion focuses on the following semiconductors: Si, GaAs, InP, and II-VI compounds based on the Cd-(chalcogenide) materials.     

Quantum Tomography under Prior Information

We provide a detailed analysis of the question: how many measurement settings or outcomes are needed in order to identify an unknown quantum state which is constrained by prior information? We show that if the prior information restricts the possible states to a set of lower dimensionality, then topological obstructions can increase the required number of outcomes by a factor of two over the number of real parameters needed to characterize the set of all states. Conversely, we show that almost every measurement becomes informationally complete with respect to the constrained set if the number of outcomes exceeds twice the Minkowski dimension of the set. We apply the obtained results to determine the minimal number of outcomes of measurements which are informationally complete with respect to states with rank constraints. In particular, we show that the minimal number of measurement outcomes (POVM elements) necessary to identify all pure states in a d-dimensional Hilbert space is 4d?3?c(d) α(d) for some ${c(d)\in[1,2]}$ and α(d) being the number of ones appearing in the binary expansion of (d?1).