Chromium complexes ligand field states

Gnmwald-Winstein analysis, 505 Chromium(III) complexes doublet excited states reactions, 400 emission rules, 395 ligand field states reactivity, 397 magnetic behavior, 272 mixed-ligand reactivity, 398 nitrito... 

It will not have escaped the reader s attention that the kinetically inert complexes are those of (chromium(iii)) or low-spin d (cobalt(iii), rhodium(iii) or iridium(iii)). Attempts to rationalize this have been made in terms of ligand-field effects, as we now discuss. Note, however, that remarkably little is known about the nature of the transition state for most substitution reactions. Fortunately, the outcome of the approach we summarize is unchanged whether the mechanism is associative or dissociative. 

Term labels appropriate for d3 and d6 configurations in octahedral ligand fields will be used in this review to designate the ligand field or d-d excited states of cobalt(III) and chromium(III) complexes. This... 

Luminescence spectrocopy is potentially a powerful technique for studying chromium(III) complexes and a series of fluoro and aqua complexes have been studied.1066 The luminescence correlates well with ligand field strength and, at. liquid air temperatures, the lifetime of the doublet state from which phosphorescence originates is 2 x 1CT7 s 1. 

It has already been stated that chromium complexes of tridentate metallizable azo compounds occupy their position as the single most important class of metal complex dyestuffs because of their high stability. It should be noted, however, that in this context the term stability is not used in the thermodynamic sense but relates to the kinetic inertness of the complexes.25 Octahedral chromium(III) complexes have a tP electronic configuration and the ligand field stabilization energy associated with this is high.26 Ligand replacement reactions involve either a dissociative... 

This work lead to an interest in the luminescence of lower symmetry chromium ammine complexes. In these complexes, the 2Eg state is split into two components by the lower symmetry ligand field. The tetragonal ligand field parameters for many of these compounds were well known or easily available from optical spectroscopy, but the splitting of the 2Eg as measured by the absorption and emission spectroscopy... 

Luminescence is observed from coordination complexes of first row transition metals less often than from complexes of second or third row metals. This is a result of the presence of low-energy ligand field (LF) states into which the excitation is funneled that can rapidly deactivate through either non-radiative pathways to the ground state or photo-reaction pathways to products. Recent reports relating to the luminescence of titanium," chromium", and zinc complexes provide examples of new emissive first row coordination compounds. 

The electronic states of chromium(III) complexes in an octahedral (Oh) ligand field are shown in Fig. 2.1. The ground state tig has a " A2g term, and the excited state tlgcl has l2g and " T g(F) terms. Since this transition corresponds to... 

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