Ring compounds chelate rings

Compound Chelate ring O-Sn Sn—Xax OSnXax OSnCeq ASn Reference... 

Most mordant dyes are monoazo stmctures. The most important feature of this class of dyes is excellent fastness to light and washing. Mordant dyes are available ia aU shades of the spectmm with the exceptioa of bright violets, blues, and greens. To be useful, the metal complexes must be stable, ie, must not demetallize when subjected to dyebath conditions and aU aftertreatment processes, especially repeated washings. Chromium forms stable chelate rings with mordant dyes which are not affected by treatment with either weak acid or alkaU (see Coordination compounds). 

Compound [PtCl( Bu2PCMe2CH2)2l reacts with pyrazole or 3,5-dimethyl-pyrazole in the presence of sodium hydroxide to form 242 (R = H, Me) [84ICA (82)L9]. The chelate ring is not planar in this case, and the trans strucmre of the pyrazolate derivative was demonstrated. Tlie four-coordinated platinum atoms are characterized by a distorted square-planar coordination. 

In chelation complexes (sometimes called inner complexes when uncharged) the central metal ion coordinates with a polyfunctional organic base to form a stable ring compound, e.g. copper(II) acetylacetonate or iron(III) cupferrate ... 

Reaction of the diphosphines Ph2P(CH2) PPh2 (n = 1-3) with MCl2(PhCN)2 affords 1 1 m-complexes (Figure 3.46) [102]. (Note the use of the labile PhCN adducts if the MCl salts are used, Magnus type compounds M(P-P)2+MCl4- are formed.) Similar complexes are formed with other halides for the thiocyanates see section 3.8.6. The structures of the palladium complexes have been determined (Table 3.10) with square coordination only achieved for n = 3 with the formation of a six-membered metal-chelate ring. 

It is believed [1135,1136] that the decomposition of metal complexes of salicyaldoxime and related ligands is not initiated by scission of the coordination bond M—L, but by cleavage of another bond (L—L) in the chelate ring which has been weakened on M—L bond formation. Decomposition temperatures and values of E, measured by several non-isothermal methods were obtained for the compounds M(L—L)2 where M = Cu(II), Ni(II) or Co(II) and (L—L) = salicylaldoxime. There was parallel behaviour between the thermal stability of the solid and of the complex in solution, i.e. Co < Ni < Cu. A similar parallel did not occur when (L—L) = 2-indolecarboxylic acid, and reasons for the difference are discussed... 

In nickel and palladium dithiobenzoato complexes, four-membered chelate rings are formed (366), whereas, in the corresponding phenyl-dithio acetates [M2(S2CCH2Ph)4], the dithio ligands act as bridging groups between the two metal atoms, with the formation of binuclear units (367). The molecular structure of the latter compounds shows that each metal atom is coordinated to four sulfur atoms and to the other metal atoms in a square-pyramidal geometry. Other evidence for... 

As already mentioned, the macrocyclic ring can be further enhanced if the propylene moiety is substituted by a butylene group. Visible spectral data of a series of related compounds [Cu(L BF2)D]X 132 and the structural study of the derivative with D = H2O show that the seven-membered chelate ring influences the structure and other properties like electronic absorption of the copper(II) complex [193]. 

Figures 2,3,5, and 6 show anionic compounds 5 to 22 and 25 to 30, which have been described in the literature since 1997. In these adducts, as in examples 1 to 4, the P(VI) derivatives have carbon or oxygen atoms in the immediate proximity of the central (pseudo-)octahedral atom. This is probably due to the accessibility of the ligand precursors, the ease of their manipulation and, more importantly, to the sheer strength of the resulting P-C and P-0 bonds. They all present tris(bidendate) structures in which the three chelating rings can be identical (Fig. 2 and most of Fig. 6) or of two different types (Fig. 3). The ligands can be monooxo (Fig. 6) or dioxo (Fig. 2 and Fig. 3). These differences in composition have, of course, consequences for the making of the derivatives.

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. 

Structures of coordination compounds suggest that smaller chelate rings promote higher coordination numbers. Twelve coordination... 

The platinum(0) complex [Pt(PhNO)(PPh3)2] reacts with C02 to afford the metallacyclic nitroso species [Pt 0N(Ph)C(0)0 (PPh3)2] (60), the first example of insertion of C02 into a Pt—N bond.186 Other unsaturated carbon compounds such as CS2 and electrophilic alkenes and alkynes react similarly. The diradical peril uoro-/V,/V -dimethylethane-l,2-bis(amino-oxyl) reacts readily by oxidative addition to the platinum(0) precursor Pt(PPh3)4 to afford the corresponding platinum(lI)-nitroso complex containing a seven-membered chelate ring (61). The resulting complex is stable in air for several days at room temperature.187... 

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