Infrared spectroscopy transition metal complexes

Thiazyl monomer is a radical with one unpaired electron. It exhibits an IR band at 1209 cm-1. The experimental dipole moment is 1.83 0.03 D in the opposite direction to that in NO (p = 0.16 D). Much less is known about selenazyl monomer, SeN, but it has been characterized by infrared spectroscopy.36 The structure of a transition-metal complex [OsTp(NSe)Cl2] (Tp=hydrotris(l-pyr-azolyl)borate) has been determined.39... 

Fourier-transform infrared (FTIR) spectroscopy Spectroscopy based on excitation of vibrational modes of chemical bonds in a molecule. The energy of the infrared radiation absorbed is expressed in inverse centimeters (cm ), which represents a frequency unit. For transition-metal complexes, the ligands -C N and -C=0 have characteristic absorption bands at unusually high frequencies, so that they are easily distinguished from other bonds. The position of these bonds depends on the distribution of electron density between the metal and the ligand an increase of charge density at the metal results in a shift of the bands to lower frequencies. 

Infrared data have been tabulated for benzotriazole and a wide range of its transition metal complexes or adducts (172). Far infrared spectra have been recorded for copper(II) benzotriazole adducts and bands at 270-320 cm-1 have been assigned to Cu-N vibrations (172). Infrared absorptions at approximately 825, 800, and 775 cm-1 in the spectra of cobalt(III)/4,5-disubstituted triazolate complexes have been attributed to triazolate ring vibrations (109). Infrared data have been reported and assignments made for palladium and platinum thiatriazoline-5-thionate complexes (37) and for the parent thione (127). Vibrational spectroscopy has been employed in an attempt to determine coordination sites for a range of 8-azapurine complexes (108). 

Infrared and UV/vis data have been used by several authors to identify the C=C, C=0, and M—O stretches in the complexes synthesized 15, 18-21, 37, 38, 41, 44, 50, 54, 56, 58, 59, 64-66, 69, 74, 78, 80, 82, 103). Except in the initial research on first-row transition metal complexes of squaric acid, where these data were used in proposing structures, IR and UV/vis analysis have been used as supporting evidence for the particular coordination mode of the ligand 19,21,22, 45, 52, 59, 65). Infrared spectroscopy has also been utilized in the study of mixed oxalate/squarate complexes 118), although not to the same extent as in complexes of the oxalate ion. For example, Scott et al. studied the IR properties of Co(III) oxalate complexes with the hgand in a variety of chelating/bridging situations 119). 

Weber WA, Gates BC (1997) Hexarhodium clusters in NaY zeolite Characterization by infrared and extended X-ray absorption fine structure spectroscopies. J Phys Chem B 101 10423 Goellner JF, Gates BC, VayssUov GN, Rosch N (2000) Structure and bonding of a site-isolated transition metal complex Rhodium dicarbonyl in highly dealuminated zeolite Y. J Am Chem Soc 122 8056... 

Transition metal coordination of Cu(II) carboxylate groups and pyridine groups was employed as a means of coupling a telechelic butadiene-base polymer with a randomly functionalized styrenic polymer. Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) indicated partial miscibility of the two polymers and Fourier transform infrared (FTIR) spectroscopy demonstrated that interactions occurred on a molecular level. When compared with blends of PSVP and the free acid derivative of CTB, the compositions based on the transition metal complex had improved dimensional stability at elevated temperatures, though there remains some question as to the stability of the copper salt to hydrolysis. Electron spin resonance (ESR) spectroscopy showed that only the... 

Two major fillers used in the rubber industry are silica and carbon black. Carbon black is black because it absorbs/scatters all radiation, including infrared, impinging on it. Hence, simple transmission spectroscopy of carbon black filled specimens is not straightforward and is usually not possible unless the samples are very thin. Carbon black filled samples have not been readily examinable using micro-spectroscopic methods. Silica filled systems are more amenable to microscopic techniques [76] and can be examined to determine silica-polymer(rubber) interactions. The presence of inorganic materials, e.g., transition metal complexes in... 

A well-developed series of complexes with rich MLCT excited-state behaviour are Re(I)-diimine complexes. [Re(bpy)(CO)3Cl] was the first transition metal complex used as a catalyst for CO2 reduction to CO, proposed by Lehn and Ziessel [41]. This series of complexes is particularly amenable to study of the excited state by time-resolved infrared spectroscopy. Formation of the MLCT Re bpy excited state leads to a reduction of the electron density on the metal centre. Consequently, d n backbonding from Re ti-orbitals to the antibonding n orbitals of CO ligands is reduced, resulting in an increase of the energy of the stretching vibrations, v(CO), by several tens of wavenumbers in the excited state if... 

Note the ground-state atomic term symbol for Cr is F, which splits into T2, Ti and A2 for an octahedral transition metal complex. For more information regarding term symbol notation and absorption spectra for transition metal complexes, see Shiiver et al. Inorganic Chemistry, 4th ed., W. H. Freeman New York, 2006. http //www.scribd.com/doc/6672586/Electronic-Spectroscopy-l Note excited electrons give off their energy via infrared emission and thermal interactions with the corundum crystal lattice, referred to as electron-phonon (lattice vibrations) interactions. 

High pressure infrared (HP IR) spectroscopy has now been used for over 30 years for the study of homogeneous transition metal catalysed processes. The technique is particularly useful for reactions involving carbon monoxide, for which transition metal carbonyl complexes are key intermediates in the catalytic mechanisms. Such complexes have one or more strong r(CO) absorptions, the frequencies and relative intensities of which provide information about the geometry and electronic character of the metal center. As well as probing the metal species, HP IR spectroscopy can also be used to monitor the depletion and formation of organic reactants and products if they have appropriate IR absorptions. 

The structural and spectral complexity of clay minerals is sufficient to consider a single mineral as a multicomponent mixture in itself. Detectible by near infrared spectroscopy are adsorbed water and structural hydroxyls (25.) exchangeable and structural transition metal cations (2fL and this work), adsorbed species including atmospheric gases (22), organic materials (2) accessory minerals (2SL) and, possibly, trapped hole centers (0 -centers). Thus it is of interest to adapt NIRA to studies of mineral surface activity. We have done this by examination of a small set of highly homologous clays in which laboratory control of only one variable at a time could be accurately achieved and independently confirmed. 

Grills DC, Huang KW, Muckerman JT, Fujita E. Kinetic studies of the photoinduced formation of transition metal-dinitrogen complexes using time-resolved infrared and UV-visible spectroscopy. Coord Chem Rev 2006 250 1681-95. 

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