Ligand bonding energies

K has been identified as CFl200I-I from its chemistry the reaction mechanism is insertion [115], Collision-induced dissociation (in a SIFT apparatus, a triple-quadnipole apparatus, a guided-ion beam apparatus, an ICR or a beam-gas collision apparatus) may be used to detemiine ligand-bond energies, isomeric fomis of ions and gas-phase acidities. 

In the gas phase, ions may be isolated, and properties such as stability, metal-ligand bond energy, or reactivity determined, full structural characterization is not yet possible. There are no complications due to solvent or crystal packing forces and so the intrinsic properties of the ions may be investigated. The effects of solvation may be probed by studying ions such as [M(solvent) ]+. The spectroscopic investigation of ions has been limited to the photoelectron spectroscopy of anions but other methods such as infrared (IR) photodissociation spectroscopy are now available. 

Thermochemical measurements have been made in an attempt to establish )(Mo=Mo). The interpretation of the data is dependent upon assumptions of the relevant metal-ligand bond energies and, in view of these uncertainties, ranges of values have been quoted 592 196 kJ mol-1 for [Mo2(NMe2)6] and 310-395 kJ mol-1 for [Mo2(OPri)6].203 MO calculations have indicated that the strength of the Mo—Mo triple bond is affected significantly by the nature of the attached ligands and n donors, such as NH2) stabilize this bond. 

One of the first examples from our laboratory [13] which suggested that photodissociation thresholds could yield quantitative metal-ligand bond energies was from a comparison of the photodissociation spectra of FeOH+ and FeC0+ obtained by monitoring reactions 9 and 10, respectively, and shown in Figure 3 The two spectra are remarkably similar with two absorption maxima observed... 

Metal-Ligand Bond Energies. In an analogous fashion, the removal of an electron (oxidation) from water via Eq. (10.2) is aided by the presence of transit -metal ions [e.g., Cu fOH e, Fen(OH2)6+, and Cem(OH2)6+, each with one, two, and three M—OH2+ covalent bonds, respectively] ... 

Table 10.7 summarizes the copper-ligand bond energies for the various complexes. 

The redox data of Tables 13.1-13.4 can be used to estimate the metal-ligand bond energies for (ClgTPP)A/mL complexes, as, for instance, for (ClgTPP)Fem—OH 18... 

The results from the estimation of covalent bond energies from ligand-centered redox potentials for several iron and manganese compounds are compared to gas-phase values in Table 3-10. 23,24 xhg self-consistency is impressive, and indicates that the iron-ligand bond energy is reduced (1) by... 

Perhaps the most popular has been the hybride functional B3LYP [78] by Becke in which 20% of YP is replaced by AFS. We present in Table 3 a number of metal-ligand distances optimized by B3LYP [88]. For most systems, the error is only 0.02 A. In Table 4, we compare metal-ligand bond energies calculated by BLYP [76, 81] and B3LYP [76, 80]. Obviously, B3LYP represents a clear improvement over BLYP. 

A steady decrease in Kt values with increasing i is to be expected provided there are only slight changes in the metal—ligand bond energies as a function of /, which is usually the case. For example, in the Ni2+-NH3 system to be discussed below, the enthalpies of the successive reactions Ni(NH3), 1 +NH3 =Ni(NH3) are all within the range 16.7-18.0 kJ mol-1. 

Platinum-ligand and palladium-ligand bond energies. C. T. Mortimer, Rev. Inorg. Chem., 1984, 6, 233 (50). 

Importance of Metal—Ligand Bond Energies in Organometallic Chemistry An Overview... 

The acquisition and analysis of metal-ligand bond energy information in organometallic molecules represents an active and important research area in modern chemistry. This overview begins with a brief historical introduction to the subject, followed by a discussion of basic principles, experimental methodology, and issues, and concludes with an overview of the Symposium Series volume organization and contents. 

MARKS Metal-Ligand Bond Energies in OrganometaUic Chemistry 5... 

Another class of gas phase experiments begins with the molecular organometallic compounds of interest and measures the added energy required for ligand dissociation. The mass spectrometric appearance potential method relates the metal-ligand bond energy to the mass... 

MARKS Metal—Ligand Bond Energies in OrganometaUic Chenustry... 

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