Ligand environments

Besides structure and substructure searches, Gmclin provides a special search strategy for coordiuation compouuds which is found in no other database the ligand search system, This superior search method gives access to coordination compounds from a completely different point of view it is possible to retrieve all coordination compounds with the same ligand environment, independently of the central atom or the empirical formula of the compound. 

Thus, if the change of the ligand environment results in an increase of the ir-complcx stability, the rise of the propagation rate constant up to the value Kv will be observed according to the following ... 

Resonance Raman studies of the recombinant proteins showed vibrational bands at the 200-430 cm region characteristic of iron-sulfur clusters (124). Most interestingly, on Fe and O isotope sensitive band was detected at 801 cm which could be attributed to either a Fe(IV)=0 species or a monobridged Fe-O-Fe structure. This observation, together with Mossbauer analysis, which indicated a mixed N, 0, and S ligand environment for cluster 2, suggests a Fe-O-Fe or Fe=0 unit as part of the structure for cluster 2. 

The crystallographic structure of the D. vulgaris protein has been reported by Lindley and collaborators (132). The structure was solved to a resolution of 1.7 A. The major findings are consistent with most of the conclusions derived from the Mossbauer work done in the D. desulfuricans protein. The protein was found to contain two distinct clusters of the same nuclearity. Also, one cluster has a mixed N, O, S ligand environment, while the other has a regular iron-sulfur core... 

Using 1,4,8,11-tetraazacyclotetradecane, the structure of complex (800) (distorted trigonal planar Cu-Cu 6.739 A) was determined. Reactivity with 02 was investigated to demonstrate the formation of trans-l,2-peroxo species.585 As part of their work with copper(I) complexes with 02, the structure of a dicopper(I) complex ((801) distorted tetrahedral 7.04 A), supported by macrocyclic ligand environment, was reported by Comba and co-workers. Tolman and co-workers structurally characterized a three-coordinate copper(I)-phenoxide complex (802) (planar T-shaped) that models the reduced form of GO.587 The copper(I) analogue [Cu(L)][CF3-SO3]-0.43MeOI I (803) of a copper(II) complex (534) was also reported to demonstrate the role of ligand framework conformability in CV /Cu1 redox potentials.434 Wilson and co-workers... 

When a lanthanide ion is placed in a ligand environment with symmetry lower than spherical, the energies of its partly filled 4f orbitals are split by the electrostatic field of the ligand. The result is a splitting of the 2/ + 1 degeneracy of the free ion states (see Figure 1.2). 

The total rate constant kexp = kK weakly depends on the hydrocarbon residue, which is seen from the data collected in Table 10.3. However, the ligand environment, as well as the solvent, has a substantial effect on the k value [4—9]. 

Asymmetry in the ligand environment, either geometric or in charge distribution (or both), affect the asymmetry parameter, tp An r = 0 value corresponds to complete axial symmetry, whereas r = 1 corresponds to pure rhombic symmetry. Electric monopole interactions between the nuclear charge distributions and the electrons at the nucleus cause a shift of the nuclear ground and excited states. These interactions are known as the isomer shift, 8. Both the Mossbauer source and the absorber (the sample of interest) experience an isomer shift, and it is customary to quote 8 relative to a standard, usually Fe metal or Na2[Fe(CN)5NO] 2H2O at... 

The nature of the ligand donor atom and the stereochemistry at the metal ion can have a profound effect on the redox potential of redox-active metal ions. The standard redox potentials of Cu2+/Cu+, Fe3+/Fe2+, Mn3+/Mn2+, Co3+/Co2+, can be altered by more than 1.0 V by varying such parameters. A simple example of this effect is provided by the couple Cu2+/Cu+. These two forms of copper have quite different coordination geometries, and ligand environments, which are distorted towards the Cu(I) geometry, will raise the redox potential, as we will see later in the case of the electron transfer protein plastocyanin. 

Exchange of varying quantities of the oxovanadium(IV) ion on Mg hectorlte resulted In hydrolysis of V at low levels of adsorption (53). The hydrolyzed product that was adsorbed on the clay surface was interpreted as having a ligand environment that was partially aqueous and partially hydroxide in nature. With increasing V... 

Only in the case of Na -beidellite were at least two different ligand environments of Cu + evident from the ESR spectra (Figure 17). This may indicate interstratification and the existence of interlayers with one and two layers of water. The g-values and hyperfine splittings for the rigid-limit spectra of Figures 15-17, as well as for previously studied minerals ( 7), are given in Table IV. 

IR-cell can be used as an on-line detector connected to a reaction vessel. Both techniques play an important role in the study of the variation of the ligand environment of the catalytic complexes in a controlled manner. Both IR and NMR spectroscopy can be used at high pressure in dedicated tubes or cells. The specific advantages and disadvantages of both techniques are summarised below ... 

Initially, it was thought more likely that the electron poor metal atom would be involved in the electrophilic attack at the alkene and also the metal-carbon bond would bring the alkene closer to the chiral metal-ligand environment. This mechanism is analogous to alkene metathesis in which a metallacyclobutane is formed. Later work, though, has shown that for osmium the actual mechanism is the 3+2 addition. Molecular modelling lends support to the 3+2 mechanism, but also kinetic isotope effects support this (KIEs for 13C in substrate at high conversion). Oxetane formation should lead to a different KIE for the two alkene carbon atoms involved. Both experimentally and theoretically an equal KIE was found for both carbon atoms and thus it was concluded that an effectively symmetric addition, such as the 3+2 addition, is the actual mechanism [22] for osmium. 

---