Chelate ring five-membered

Mo(CO )4j2 (PhjPIOjSiOslPPhz) 2 pour-membered chelate ring. Five-membered chelate ring. 

In Table 42, in complexes with SBs (97)-(99), the / values of compounds with n = 2 (n in R = (CH2) ) are larger than with n = 3. This suggests that the antiferromagnetic exchange interaction is stronger with n = 2, and this has been attributed to the difference in the chelate ring (five- or six-membered).775 For n-2, the J values also depend appreciably on the nature and position of the Hsal substituent for n - 3, they are relatively insensitive to ring substituents.358... 

NHJ,[U0,(C20J3] 242 2.43(C20, five-membered chelate ring) four-membered chelate ring) 1.69(U=0) Eight-co-ord. hexagonal bipyramid, see formula (12) ... 

This type of tautomerism is principally important for the preparation of chelates with five-membered metallacycles of composition MN2S2 from benzothiazoline-ligating compounds (Equation (16)). Ring-chain... 

Particularly alkyl halides which have a perfluoroalkyl group at the /3-position undergo smooth carbonylation. Probably the coordination of fluorine to form a five-membered chelate ring accelerates the reaction. Double carbonylation to give the a-keto amide 915 is possible in Et NH with the fluorine-bearing alkyl iodide 914[769,770]. The ester 917 is obtained by the carbonylation of the /3-perfluoroalkyl iodide 916 in ethanol. 

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. 

When, however, the ligand molecule or ion has two atoms, each of which has a lone pair of electrons, then the molecule has two donor atoms and it may be possible to form two coordinate bonds with the same metal ion such a ligand is said to be bidentate and may be exemplified by consideration of the tris(ethylenediamine)cobalt(III) complex, [Co(en)3]3+. In this six-coordinate octahedral complex of cobalt(III), each of the bidentate ethylenediamine molecules is bound to the metal ion through the lone pair electrons of the two nitrogen atoms. This results in the formation of three five-membered rings, each including the metal ion the process of ring formation is called chelation. 

However, EDTA has the widest general application in analysis because of its powerful complexing action and commercial availability. The spatial structure of its anion, which has six donor atoms, enables it to satisfy the coordination number of six frequently encountered among the metal ions and to form strainless five-membered rings on chelation. The resulting complexes have similar structures but differ from one another in the charge they carry. 

Ring size. Five- or six-membered conjugated chelate rings are most stable since these have minimum straia The functional groups of the ligand must be so situated that they permit the formation of a stable ring. 

The X-ray crystallographic analysis of the unsymmetrical BisP shows a strong distortion of the five-membered chelation ring as compared to that of symmetric BisP [32]. The large difference in the steric repulsions between the bulky substituent borne on one phosphorus atom and the neighboring atoms on the one hand and the other (different) bulky substituent borne on the other phosphorus atom and the same neighboring atoms on the other hand is believed to be responsible for better steric matching with some substrates. 

As mentioned, stabilization of neutral hexacoordinated phosphorus via nitrogen donation is possible and this topic has been widely studied in the past few years. As P-N bonds are weaker and longer than those of P-C and P-0, chemists have essentially relied on chelation to enforce their formation. Most structures involve five- and six-membered chelating rings and the compounds that have been reported are described in Schemes 7,8, and 9 and Figs. 7 and 8. 

The chelate ring size principle can have structural effects as well as effects on thermodynamic stability in aqueous solution. An example is coordination of metal ions by sugars (44). The cyclic polyol cts-inositol can coordinate metal ions in two distinct ways (Fig. 14) (45). In ax-ax-ax bonding (Fig. 14), the metal ion is part of three fused six-membered chelate rings. Alternatively, in ax-eq-ax coordination, the metal ion is part of two fused five-membered and one six-membered chelate rings. Angyal has noted that metal ions of radius more than 0.8 A adopt the ax-eq-ax structure (44), whereas with an ionic radius... 

In the four-coordinate complexes (12) (X = Cl, Br) the phenol phosphine is coordinated as a monodentate.151 In the presence of base, the phenolate O atom deprotonates and coordinates to give (13). The five-membered chelate ring in this complex is resistant to protonation, and ringopening is not observed even in the presence of CO or C2H4. 

Ligands with S donors in addition to N and or O donors bound to Co11 are reasonably large in number. For example, the 4-amino-3-alkyl-l,2,4-triazole-5-thione can bind Co11 as a chelate employing the primary amine and thione substituents on the five-membered ring,510 whereas the trifluoromethyl ligand (afmt) forms [Co(afmt)2(H20)2](N03)2, defined as the A -irons isomer... 

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