Coordination compounds metal-ligand bond

Four-coordinate complexes exhibit lower isomer shifts than six-coordinate compounds. Metal-ligand bonds are shorter and more covalent if the coordination number is smaller because of less steric hindrance and less overlap with antibonding 2g orbitals in the case of four as compared to six bonds. 

The mutual influence of ligands in transition metal coordination compounds with multiple metal-ligand bonds. E. M. Shustorovich, M. A. Porai-Koshits and Y. A. Buslaev, Coord. Chem. Rev., 1975,17,1-98 (345). 

Two other publications on Ir (73 keV) Mossbauer spectroscopy of complex compounds of iridium have been reported by Williams et al. [291,292]. In their first article [291], they have shown that the additive model suggested by Bancroft [293] does not account satisfactorily for the partial isomer shift and partial quadrupole splitting in Ir(lll) complexes. Their second article [292] deals with four-coordinate formally lr(l) complexes. They observed, like other authors on similar low-valent iridium compounds [284], only small differences in the isomer shifts, which they attributed to the interaction between the metal-ligand bonds leading to compensation effects. Their interpretation is supported by changes in the NMR data of the phosphine ligands and in the frequency of the carbonyl stretching vibration. 

The most common reaction exhibited by coordination compounds is ligand substitution. Part of this chapter has been devoted to describing these reactions and the factors that affect their rates. In the solid state, the most common reaction of a coordination compound occurs when the compound is heated and a volatile ligand is driven off. When this occurs, another electron pair donor attaches at the vacant site. The donor may be an anion from outside the coordination sphere or it may be some other ligand that changes bonding mode. When the reaction involves an anion entering the coordination sphere of the metal, the reaction is known as anation. One type of anation reaction that has been extensively studied is illustrated by the equation... 

Fourier transformation of Cu EXAFS data gathered on the Cu(MPG) complex reveals two separate peaks representing shells at distances of 1.9 and 2.3 A. When tested for Ns (coordination number), metal-ligand distance (R as), and Debye-Waller parameter difference (Aa2as) followed by comparison to known model compounds, results show that the presence of both a Cu-(N, O) and Cu-S shell is necessary to obtain an adequate fit to the EXAFS data. Therefore it was concluded that a Cu-S bond is present in the compound. 

Table 5-10 Metal-Ligand Bond Distances in Transition-Metal Coordination Compounds... 

See, R. F., Kruse, R. A., and Strub, W. M. (1998). Metal-ligand bond distances in first-row transition metal coordination compounds Coordination number oxidation state and specific ligand effects. Inorg. Chem. 37, 5369-75. 

The peculiarities of classical localized coordination bonds (two-electron and two-center [1,4,5]) are displayed most clearly in MCC. Mostly, the elements of the first period of the Periodic Table (C, N, O) participate as electron donors in the formation of such bonds. In complexes of this type, the role of Ji-dative interactions is significant. These interactions are revealed in coordination compounds of ligands containing the elements of the next periods as donor centers (P, As, Sb S, Se, Te Cl, Br, I). We note that the examined complexes are the most successful objects to study the influence of ligand and metal nature on the character of the coordination bond, since, in this case, the factors which could distort this influence (chelate, macrocyclic, and other effects [117,135]) are absent. 

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