Reactivity of the Bicyclic Amido-Substituted Silicon(I) Ring Compound Si4{N(SiMe3)Mes}4 with FLP-Type Character

The bicyclic amido-substituted silicon(I) ring compound Si₄{N(SiMe₃)Mes}₄ 2 (Mes=Mesityl=2,4,6-Me₃C₆H₂) features enhanced zwitterionic character and different reactivity from the analogous compound Si₄{N(SiMe₃)Dipp}₄ 1 (Dipp=2,6-ⁱPr₂C₆H₃) due to the smaller mesityl substituents. In a reaction with the N-heterocyclic carbene NHC (1,3,4,5-tetramethyl-imidazol-2-ylidene), we observe adduct formation to give Si₄{N(SiMe₃)Mes}₄ ⋅ NHC ( 3 ). This adduct reacts further with the Lewis acid BH₃ to yield the Lewis acid–base complex Si₄{N(SiMe₃)Mes}₄ ⋅ NHC ⋅ BH₃ ( 4 ). Coordination of AlBr₃ to 2 leads to the adduct 5 . Calculated proton affinities and fluoride ion affinities reveal highly Lewis basic and very weak Lewis acidic character of the low-valent silicon atoms in 1 and 2 . This is confirmed by protonation of 1 and 2 with Brookharts acid yielding 6 and 7 . Reaction with diphenylacetylene only occurs at 111 °C with 2 in toluene and is accompanied by fragmentation of 2 to afford the silacyclopropene 8 and the trisilanorbornadiene species 9 .     

A silica-based monolithic column in capillary HPLC and CEC coupled with ESI-MS or electrospray-atmospheric-pressure laser ionization-MS

We describe the successful coupling of CEC and capillary HPLC with the recently developed atmospheric-pressure laser ionization (APLI) method. APLI is suitable for selectively and sensitively ionizing nonpolar aromatic compounds at ambient pressure for subsequent mass-selective detection. The polycyclic aromatic hydrocarbons used as analytes are first separated either by CEC on a silica-based monolithic column or by capillary HPLC. The eluent, along with a sheath flow, is volatilized by microelectrospray and then selectively ionized by excimer laser (KrF*) radiation via two-photon excitation. A QTOF-MS is used as mass-selective detector. This interface combination makes soft ionization of thermally labile nonpolar aromatic analytes possible.     

Syntheses and X-ray Characterization of Novel [M4(H2O)2(XW9O34)2] n− (M=CuII, X=CuII; and M=FeIII, X=FeIII) Polyoxotungstates

Two novel examples of sandwich type heteropolyanions were synthesized and characterized by X-ray crystal structure and elemental analysis as well as infrared spectroscopy. Na₁₃[H₃Cu₄(H₂O)₂(CuW₉O₃₄)₂]39H₂O (1) and Na₉K[Fe₄(H₂O)₂(FeW₉O₃₄)₂]32H₂O (2) were prepared in aqueous solution by reaction of sodium tungstate with Fe^III and Cu^II cations, respectively. 1 crystallizes in the monoclinic space group P2₁/n (a=13.054(3) Å, b=17.729(4) Å, c=20.998(4) Å, =93.50(3)°), while 2 is triclinic, space group P¯1 (a=12.316(2) Å, b=13.716(3) Å, c=14.925(3) Å, =99.36(3)°, =104.21(3)°, =101.55(3)°). Each anion consists of two [XW₉O₃₄] ^n– moieties (X=Fe^III, n=11 (1) and Cu^II, n=12 (2)) which can be described as -B-isomers of the defect Keggin anion. These units are linked via a belt of four Fe^IIIO₆ or Cu^IIO₆ groups. Two transition metal atoms fill their octahedral coordination sphere with one additional water ligand.     

Absolute graphs with prescribed endomorphism monoid

We consider endomorphism monoids of graphs. It is well-known that any monoid can be represented as the endomorphism monoid M of some graph Γ with countably many colors. We give a new proof of this theorem such that the isomorphism between the endomorphism monoid $\mathop{\rm End}\nolimits (\Gamma)We consider endomorphism monoids of graphs. It is well-known that any monoid can be represented as the endomorphism monoid M of some graph Γ with countably many colors. We give a new proof of this theorem such that the isomorphism between the endomorphism monoid and M is absolute, i.e. holds in any generic extension of the given universe of set theory. This is true if and only if |M|,|Γ| are smaller than the first Erdős cardinal (which is known to be strongly inaccessible). We will encode Shelah’s absolutely rigid family of trees (Isr. J. Math. 42(3), 177–226, 1982) into Γ. The main result will be used to construct fields with prescribed absolute endomorphism monoids, see G?bel and Pokutta (Shelah’s absolutely rigid trees and absolutely rigid fields, in preparation). This work was supported by the project No. I-706-54.6/2001 of the German-Israeli Foundation for Scientific Research & Development and a fellowship within the Postdoc-Programme of the German Academic Exchange Service (DAAD).     

Investigation of lifetimes in dipole bands of 142Gd

Lifetimes have been measured for dipole bands in ¹⁴²Gd using DSAM. The deduced B(M1) and B(E2) values as well as B(M1)/B(E2) ratios are compared with calculations in the framework of the TAC (Tilted Axis Cranking) and SPAC (Shears mechanism with Principal Axis Cranking) models. The dipole bands DB1 to DB4 can be interpreted as magnetic rotational bands.     

The normal subgroup lattice of 2-transitive automorphism groups of linearly ordered sets

Using combinatorial and model-theoretic means, we examine the structure of normal subgroup lattices N(A()) of 2-transitive automorphism groups A() of infinite linearly ordered sets (, ). Certain natural sublattices of N(A()) are shown to be Stone algebras, and several first order properties of their dense and dually dense elements are characterized within the Dedekind-completion of (, ). As a consequence, A() has either precisely 5 or at least 2²¹ (even maximal) normal subgroups, and various other group- and lattice-theoretic results follow.     

Automorphism groups of totally ordered sets: A retrospective survey

In 1963, W. Charles Holland proved that every lattice-ordered group can be embedded in the lattice-ordered group of all order-preserving permutations of a totally ordered set. In this article we examine the context and proof of this result and survey some of the many consequences of the ideas involved in this important theorem.     

The use of high-throughput synthesis and purification in the preparation of a directed library of adrenergic agents

A library of potential agonists and antagonists for adrenergic receptors was prepared using high-throughput solution-phase parallel synthesis. Traditional solution-phase reductive amination reactions followed by rapid purification by ion exchange chromatography yielded products with near-analytical purity. An array of ketones and amines, arranged in an 8 × 12 matrix, were combined to form 96 individual compounds. This revised version was published online in August 2006 with corrections to the Cover Date.