Saludimerines A and B, novel-type dimeric alkaloids with stereogenic centers and configurationally semistable biaryl axes

The first biarylic bis-morphinanedienone alkaloids, saludimerines A (3a) and B (3b), isolated from a tree of Croton flavens (Euphorbiaceae) are described. These naturally occurring dimers of the known alkaloid salutaridine are joined together via a rotationally hindered biaryl axis, giving rise to atropo-diastereomers that are configurationally stable at room temperature but slowly interconvert in methanolic solution within several days. Their structures were established by spectroscopic methods and by partial synthesis, which was achieved by a highly atropo-diastereoselective biomimetic oxidative coupling of the monomeric precursor, salutaridine. Their axial configurations were elucidated by circular dichroism (CD) investigations, which succeeded despite the fact that the two atropo-diastereomers exhibit near-identical CD spectra. This remarkable phenomenon was rationalized by quantum chemical CD calculations. The configurational assignment of saludimerines A (3a) as P-axial and B (3b) as M was corroborated by atropisomer-specific NOE interactions between protons of the one molecular half with nuclei in the other.     

Matrix isolation infrared and ab initio study of the hydrogen bonding between formic acid and water

The infrared spectra of the formic acid-water complexes isolated in argon matrices are reported. Both supersonic jet expansion and a conventional effusive source followed by trapping in solid argon at 10K are used to obtain the matrices. The experimental IR spectra are compared to the data obtained from high level ab initio (MP2) and DFT (B3LYP) calculations with 6-311++G(d,p) and aug-cc-pVTZ basis sets. The complex formation results in red shifts in the C=O and O-H stretching vibrations and a blue shift in the C-O stretching vibration of formic acid. The O-H stretching modes of water also exhibit pronounced red shifts. Both the MP2 and B3LYP calculations located three minima corresponding to cyclic HCOOH...H2O complexes with two hydrogen bond interactions. The binding energies are -10.3, -5.1, and -3.5 kcal mol(-1), respectively, for the three complexes at the MP2/ aug-cc-pVTZ level, corrected for the basis set superposition error (BSSE) using the Boys-Bernardi counterpoise scheme. Comparison of the calculated frequencies of the three complexes with the matrix IR spectrum reveals that the lowest energy complex is formed. In addition, a complex of formic acid with two water molecules is observed.     

One‐Dimensional Spin Chains from CuII Ions and 2,5‐Bis(pyrazol‐1‐yl)‐1,4‐dihydroxybenzene

The purple colored coordination polymer [1 Cu]_n was obtained from 2,5‐bis(pyrazol‐1‐yl)‐1,4‐dihydroxybenzene and CuBr₂ in aqueous ammonia. The crystal structure of [1 Cu]_n was determined from high resolution X‐ray powder diffraction data using the method of simulated annealing. In the solid state, [1 Cu]_n features largely independent linear chains, all of them being oriented parallel to the c‐axis of the crystal. The Cu ions are coordinated in a square‐planar fashion by two nitrogen atoms and two anionic oxygen donors. Magnetic susceptibility and magnetization measurements indicate the Cu ions in [1 Cu]_n to be antiferromagnetically coupled with a coupling constant of about 20 K.     

Synthesis,Structure, and Reactivity of RuII Complexes with Trimethylsilylethinylamidinate Ligands

The mononuclear amidinate complexes [(η⁶‐cymene)‐RuCl( 1a )] ( 2 ) and [(η⁶‐C₆H₆)RuCl( 1b )] ( 3 ), with the trimethylsilyl‐ethinylamidinate ligands [Me₃SiC≡CC(N‐c‐C₆H₁₁)₂]^– ( 1a^– ) and[Me₃SiC≡CC(N‐i‐C₃H₇)₂]^– ( 1b^– ) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(η⁵‐C₅H₅)Ru(PPh₃)( 1b )] ( 4a ) [(η⁵‐C₅Me₅)Ru(PPh₃)( 1b )] ( 4b ), and [(η⁶‐C₆H₆)Ru(PPh₃)( 1b )](BF₄) ( 5 ‐BF₄) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl‐silyl group using [Bu₄N]F resulted in the isolation of [(η⁶‐C₆H₆)Ru(PPh₃){(N‐i‐C₃H₇)₂CC≡CH}](BF₄) ( 6 ‐BF₄) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a / b to 6 ‐BF₄ were characterized by multinuclear NMR (¹H, ¹³C, ³¹P) and IR spectroscopy and elemental analyses, including X‐ray diffraction analysis of 1b , 2 , and 3 .     

Cationic photopolymerization with the aid of pyridinium‐type salts

Pyridinium‐type salts containing an N‐ethoxy group belong to the family of onium salts and are photoinitiators appropriate for the polymerization of monomers such as oxiranes and vinyl ethers which are not polymerizable by a free radical mechanism. The initiation is accomplished by direct or indirect (sensitized) photolysis of the onium ion, with the former being restricted to the wavelength range of self absorption, the latter being applicable at wavelengths of visible light. An additionally useful tool, namely free radical‐mediated generation of initiating species enlarges the versatility of pyridinium salts as photoinitiators. In this connection, the oxidation of free radicals by pyridinium‐type ions and the free radical‐induced fragmentation of alkoxy pyridinium ions are addressed in this article. Moreover, an interesting application is noted concerning the synthesis of novel block copolymers with the aid of the onium salt‐based photopolymerization technique.     

The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The benzyl radical ( 1 ) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix‐isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O₂ is the benzylperoxyl radical ( 2 ), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]‐H migration and subsequent cleavage of the O?O bond to produce a hydrogen‐bonded complex between the hydroxyl radical and benzaldehyde ( 4 ). Prolonged photolysis produces the benzoyl radical ( 5 ) and water, which finally yield the phenyl radical ( 7 ), CO, and H₂O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7 . Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds.     

Heavy‐Atom Tunneling in the Ring Opening of a Strained Cyclopropene at Very Low Temperatures

The highly strained 1H‐bicyclo[3.1.0]‐hexa‐3,5‐dien‐2‐one 1 is metastable, and rearranges to 4‐oxacyclohexa‐2,5‐dienylidene 2 in inert gas matrices (neon, argon, krypton, xenon, and nitrogen) at temperatures as low as 3 K. The kinetics for this rearrangement show pronounced matrix effects, but in a given matrix, the reaction rate is independent of temperature between 3 and 20 K. This temperature independence means that the activation energy is zero in this temperature range, indicating that the reaction proceeds through quantum mechanical tunneling from the lowest vibrational level of the reactant. At temperatures above 20 K, the rate increases, resulting in curved Arrhenius plots that are also indicative of thermally activated tunneling. These experimental findings are supported by calculations performed at the CASSCF and CASPT2 levels by using the small‐curvature tunneling (SCT) approximation.