Electron diffraction, reactive intermediates

Electron diffraction 2-galla- rac/ino-tetraborane, 41 218 gallaborane, 41 214 gallane vapor, 41 204-207 gallium hydrides, 41 185-188 reactive intermediates, 46 110-113 time-resolved, 46 149... 

As a result of the recognized role of transition metal hydrides as l reactive intermediates or catalysts in a broad spectrum of chemical reactions such as hydroformylation, olefin isomerization, and hydrogenation, transition metal hydride chemistry has developed rapidly in the past decade (J). Despite the increased interest in this area, detailed structural information about the nature of hydrogen bonding to transition metals has been rather limited. This paucity of information primarily arises since, until recently, x-ray diffraction has been used mainly to determine hydrogen positions either indirectly from stereochemical considerations of the ligand disposition about the metals or directly from weak peaks of electron density in difference Fourier maps. The inherent limi-... 

Transient intermediates are most commonly observed by their absorption (transient absorption spectroscopy see ref. 185 for a compilation of absorption spectra of transient species). Various other methods for creating detectable amounts of reactive intermediates such as stopped flow, pulse radiolysis, temperature or pressure jump have been invented and novel, more informative, techniques for the detection and identification of reactive intermediates have been added, in particular EPR, IR and Raman spectroscopy (Section 3.8), mass spectrometry, electron microscopy and X-ray diffraction. The technique used for detection need not be fast, provided that the time of signal creation can be determined accurately (see Section 3.7.3). For example, the separation of ions in a mass spectrometer (time of flight) or electrons in an electron microscope may require microseconds or longer. Nevertheless, femtosecond time resolution has been achieved,186 187 because the ions or electrons are formed by a pulse of femtosecond duration (1 fs = 10 15 s). Several reports with recommended procedures for nanosecond flash photolysis,137,188-191 ultrafast electron diffraction and microscopy,192 crystallography193 and pump probe absorption spectroscopy194,195 are available and a general treatise on ultrafast intense laser chemistry is in preparation by IUPAC. 

Although (7-sulfuranes had been postulated as reactive intermediates earlier, they had not been isolated <84CHEC-1(4)741>. The first stable pentacoordinated sulfur compound with four C—S bonds has now been synthesized and fully characterized <92ccii4i>. The 0-trimethylsilyl derivative (196) of dibenzothiophene S-oxide was treated at — 78 °C with 2,2 -dilithiobiphenyl. This led to (197) in 96 /o yield. The structure of (197) was fully secured by H and C NMR spectroscopy as well as by x-ray diffraction. In the solid state, it has a slightly distorted pseudotrigonal bipyramidal geometry with two apical S—C bonds, two equatorial S—C bonds, and the lone-pair electrons occupying the... 

Some studies reported enhancements in photoactivity in the presence of a small amount of rutile phase [122-124]. Even a mechanical mixture of anatase and rutile showed much higher photoactivity for naphthalene oxidation than either pnre anatase or rutile powders [123,124]. The P25 powder is produced from TiCl4 in a flow reactor [122]. Based on a detailed investigation by x-ray diffraction (XRD) and micro-Raman spectroscopy, the rutile (formed directly in the flame) was fonnd to be covered by anatase [122,124]. However, another study based on transmission electron microscopy (TEM) with selected-area electron diffraction reported the presence of separate particles of anatase and rutile in P25 [125,126]. Diffuse reflectance spectra of P25 could be reproduced by a mechanical mixture of anatase and rutile powders, and particles of pure rutile phase were isolated from P25 upon HF treatment. Photoactivity for the decomposition of 4-chlorophenol in water was compared on four commercial photocatalysts, applying criteria of (a) initial rate of pollutant disappearance, (b) amount of intermediate products formed, and (c) time necessary to achieve total mineralization [127]. Based on criterion (c), P25 was concluded to be the most efficient photocatalyst even though it contains 20% rutile and has a moderate BET surface area (ca. 50 m /g). It was also reported to have a higher photoactivity than catalyst All in the degradation of reactive black 5 (an azo-dye) [128]. 

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