Hard ligands, complexation

Coordination Complexes. The abiUty of the various oxidation states of Pu to form complex ions with simple hard ligands, such as oxygen, is, in order of decreasing stabiUty, Pu + > PuO " > Pu + > PuO Thus, Pu(Ill) forms relatively weak complexes with fluoride, chloride, nitrate, and sulfate (105), and stronger complexes with oxygen ligands (Lewis-base donors) such as carbonate, oxalate, and polycarboxylates, eg, citrate, and ethylenediaminetetraacetic acid (106). The complexation behavior of Pu(Ill) is quite similar to that of the light lanthanide(Ill) ions, particularly to Nd(Ill)... 

The i5p-titanium(IV) atom is hard, ie, not very polarizable, and can be expected to form its most stable complexes with hard ligands, eg, fluoride, chloride, oxygen, and nitrogen. Soft or relatively polarizable ligands containing second- and third-row elements or multiple bonds should give less stable complexes. The stabihty depends on the coordination number of titanium, on whether the ligand is mono- or polydentate, and on the mechanism of the reaction used to measure stabihty. 

Ligands which form stronger complexes with Class (a) metals are described as hard and those which form stronger complexes with Class (b) metals are called soft. Hard metals form more stable complexes with hard ligands and soft metals form more stable complexes with soft ligands. A listing of hard and soft metals and ligands is presented in Table 9-4. 

Thus it appears that the presence of two soft carbons on the palladium stabilizes the trans coordination of hard ligands and drives the selective coordination of ambidente ligands through their hardest atom. These results, as those described in the previous scheme, constitute other examples of the antisymbiotic effect which can be observed in soft palladium(II) complexes. 

Sugihara et al. in 1997.106 They utilized aqueous ammonium hydroxide as a reaction medium, which provided ammonia as a hard ligand to labilize the CO ligands and therefore enhance the rate of the PKR. The reaction of dicobalthexacarbonyl complexes of enynes and alkynes provided expected cyclopentenones via intramolecular and intermolecular modes respectively (Scheme 4.10). 

Cummins, Christopher C., Three-Coordinate Complexes of Hard Ligands ... 

Define monodentate, bidentate, hexadentate, ligand, complex ion, chelate, chelating agent, masking, masking agent, formation constant, coordinate covalent bond, water hardness, aliquot. 

Table 3.3 shows some stability constants for hard and soft types of metal ligand complexes. The constants are experimental values [1,2] and, as such, contain some uncertainties. Nevertheless they support well the HSAB principle. 

Fig. 2. Histogram of the formation constants of selected I 1 complexes. Formation constants generally increase with increasing metal hardness (increasing charge, decreasing ionic radius) and with increasing ligand hardness. Metal hardness increases from K+ to Zr4+ and ligand hardness from Cl " to OH". The most stable complexes are formed between hard metals and hard ligands, the weakest complexes are formed betweeen soft metals and soft ligands.

A final reason for the need for hard ligands is that it is these ligands that can form bridges to give dimeric complexes, and dimeric complexes may contribute to the catalytic activity in these reactions. The participation of dimeric species, formed for example, by... 

R = R = Cy R = 1-adamantyl, R = CfiH 5. Te2-3,5 5 ). The vanadium analogue of the latter [V N(l-Ad)(C6H3Me2-3,5) 3] " 4 has also been characterized. Furthermore, a more efficient route to [Cr N(SiMe3)2 3] and a new crystal structure determination has been described. Three-coordinate metal amides have been treated in a general review that covers three-coordinate transition metal species with hard ligands. The electronic structure and bonding in tricoordinate amido complexes of transition metals have also been detailed... 

Given the structure of InF3-3H20 (see above) and the tendency of indium(III) to be six-coordinate with hard ligands, it is reasonable that the mixed fluoro/aqua anionic complexes should also be [InF4(H20)2] and [InF5(H20)]2. This is compatible with the evidence from aqueous solution chemistry, where stability constants and thermochemical results indicate a series of [In(H20)6-nFn]l3 n)+ species.9 These complexes still await detailed systematic structural investigation. 

Soft buses will form complexes in many cases f hard ligands arc Absent iFryiuk. M. D. Haddad, T. S. Deri . D J. Coord. C/i.-h,. Rei 1990, 99. 137-212). 

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