Ethylenediaminetetraacetate ligand

More recently, Taqui Khan and co-workers (70) introduced the potentially tetradentate ethylenediaminetetraacetate ligand in the ruthenium coordination sphere in order to obtain an efficient water-soluble catalyst precursor. Indeed, starting from the ruthenium(III) aquo EDTA species [Ru(EDTA)(H20)] , carbonylation gives the paramagnetic carbonyl complex [Ru(EDTA)(CO)] which is able to induce the heterolytic activation of dihydrogen (Scheme 3). The hydroformylation of hex-l-ene performed at 50 bar (CO/H2= 1/1) and 130°C in a 80/20 ethanol-water solvent... 

In 1985, the seven-coordinate compound Ti((02CCH2)2NCH2)2)(H20) containing the hexacoor-dinate ethylenediaminetetraacetate ligand (EDTA) was structurally characterized. Similarly, the... 

Using the ladder diagram in Figure 6.7, predict the result of adding 0.080 mol of Ca + to 0.060 mol of Mg(EDTA). EDTA is an abbreviation for the ligand ethylenediaminetetraacetic acid. 

Ladder diagram for metal-ligand complexes of ethylenediaminetetraacetic add (EOTA) with Ca + and Mg +. 

The utility of complexation titrations improved following the introduction by Schwarzenbach, in 1945, of aminocarboxylic acids as multidentate ligands capable of forming stable 1 1 complexes with metal ions. The most widely used of these new ligands was ethylenediaminetetraacetic acid, EDTA, which forms strong 1 1 complexes with many metal ions. The first use of EDTA as a titrant occurred in... 

EthylenediaminetetraaceticAcid. Ethylenediaminetetraacetic acid (EDTAH has six potential donor groups two nitrogen atoms and four carboxylate groups. If EDTA 4— acts as a hexadentate ligand to a metal, the resulting complex contains five five-membered chelate rings and has a charge that is four less than that of the metal ion. 

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

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)... 

Ligands bite at one or more points. Chelants bite at two or more points, so all ligands are not necessarily chelants. Chelants forming water-soluble complexes with metal ions are called sequestrants (but not all sequestrants are chelants). The most commonly employed BW chelant, ethylenediaminetetraacetic acid (EDTA) produces coordination complexes with four points of attachment and is termed a tetraden-tate ligand. 

A chelating ligand contains two or more donor atoms in a structure that allows the ligand to wrap around the metal. Examples featured in Chapter 18 are the bidentate ligand ethylenediamine (en, chemical formula H2 NCH2 CH2 NH2) and the hexadentate ethylenediaminetetraacetate (EDTA). 

Because of the chelate effect, ligands that can displace two or more water molecules from the coordination sphere of the metal generally form stable complexes. One ligand that forms very stable complexes is the anion ethylenediaminetetraacetate (EDTA4-),... 

Two examples of polycarbonyl and polyamino compounds are shown in Figure 5.7. Ethylenediaminetetraacetic add (EDTA) is a synthetic ligand. The other, a siderophore, is biologically derived. Other polycyclic structures that coordinate with iron are also common. 

It is common for acid extracting solutions to contain ligands, such as fluoride, that, when combined with metals, increase their solubility. Chelates such as ethylenediaminetetraacetic acid (EDTA), which combine with metals and either bring them into solution or keep them in solution, are also commonly used. 

A very important ligand (or chelating agent) for titrimetric analysis is the ethylenediaminetetraacetate (EDTA) ligand. It is especially useful in reacting with calcium and magnesium ions in hard water such that water hardness can be determined. The next section is devoted to this subject. 

This last proviso is exemplified as follows. Ethylenediaminetetraacetic acid should be rendered H4edta. The ions derived from it, which are often ligands in coordination entities, are then (H3edta) , (H2edta) , (Hedta) " and (edta) ". This avoids monstrosities such as edta-H2 and edtaH 2 which arise if the parent acid is represented as edta. A list of recommended abbreviations is presented in Table 4.5. 

Numerous d cobalt(III) complexes are known and have been studied extensively. Most of these complexes are octahedral in shape. Tetrahedral, planar and square antiprismatic complexes of cobalt(lII) are also known, but there are very few. The most common ligands are ammonia, ethylenediamine and water. Halide ions, nitro (NO2) groups, hydroxide (OH ), cyanide (CN ), and isothiocyanate (NCS ) ions also form Co(lII) complexes readily. Numerous complexes have been synthesized with several other ions and neutral molecular hgands, including carbonate, oxalate, trifluoroacetate and neutral ligands, such as pyridine, acetylacetone, ethylenediaminetetraacetic acid (EDTA), dimethylformamide, tetrahydrofuran, and trialkyl or arylphosphines. Also, several polynuclear bridging complexes of amido (NHO, imido (NH ), hydroxo (OH ), and peroxo (02 ) functional groups are known. Some typical Co(lll) complexes are tabulated below ... 

---