Bidentate ligand structures

The metal complexing properties of these polyampholytes originate in the bidentate ligand structure of the base unit. Complex formation of bivalent metal ionsM with the ligand A proceeds in two successive steps. 

Reactions of the metallocene derivatives of molybdenum with pyrazole lead to the mononuclear complexes of the type 22. Structure 22 shows that it cannot be used as a ligand for the preparation of dinuclear complexes owing to geometric constraints [80JOM( 197)291 83JOM(253)53]. In acetone, an unusual complex 23 is formed [83JOM(253)53]. The bidentate ligand is the product of the reaction of pyrazole and acetone. 

Various bidentate ligands like dithiocarbamate afford monomeric square planar complexes specific examples are Pt(S2CNEt2)2 and Pt(Se2CNBu)2 (confirmed by X-ray). A similar structure is found for the dithiobenzoate Pd(S2CPh)2 one form of the dithioacetate is dimeric, a second form is a mixture of monomers and dimers. 

Coordination compounds containing bidentate ligands are often thermally more stable than those comprised of related monodentate ligands, e.g. ethylenediamine (en) complexes dissociate at a higher temperature than those of ammonia or pyridine. Compounds containing a ring structure, such as coordinated salicylaldehyde (sal) and acetyl-acetonate (acac), are particularly stable, and may often be sublimed... 

Dioximes are widely used bidentate ligands for the complexation of transition metal ions with the characteristic property to form complexes with a pseudo-macrocyclic structure if two or more of these ligands are chelating the same metal ion (119, Fig. 31) [163]. 

Coordination to the central P atom of two different types of symmetrical bidentate ligands leads to structures of type P(aa)2(bb), which are this time C2-symmetric as detailed in Fig. 16. The same chiral descriptors A and A apply to these compounds. Derivatives like 3,4,14-17 and 19-22 fit this description and have only been reported in racemic form so far. If the ligand bb is itself chiral, then diastereomers are generated. This will be described in the next section. 

The utility of thallium(III) salts as oxidants for nonaromatic unsaturated systems is a consequence of the thermal and solvolytic instability of mono-alkylthallium(III) compounds, which in turn is apparently dependent on two major factors, namely, the nature of the associated anion and the structure of the alkyl group. Compounds in which the anion is a good bidentate ligand are moderately stable, for example, alkylthallium dicar-boxylates 74, 75) or bis dithiocarbamates (76). Alkylthallium dihalides, on the other hand, are extremely unstable and generally decompose instantly. Methylthallium diacetate, for example, can readily be prepared by the exchange reaction shown in Eq. (11) it is reasonably stable in the solid state, but decomposes slowly in solution and rapidly on being heated [Eq. (23)]. Treatment with chloride ion results in the immediate formation of methyl chloride and thallium(I) chloride [Eq. (24)] (55). These facts can be accommodated on the basis that the dicarboxylates are dimeric while the... 

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). 

C20-0077. Several commercial rust removers contain the bidentate ligand oxalate, (O2 CC02) Explain how these household products remove rast. Include a structural drawing of the species that forms. 

Other classes of complexes that have been studied in depth in the Mizoroki-Heck reaction are those having a bidentate ligand containing both a NHC and a phosphine. The development of these structures was encouraged by early theoretical work from Rosch, who calculated that such ligands should be promising catalysts for this... 

CU4S4] species in which the TADDOL-derived ligand was an unexpected sul-fur-monodentate and not a S/X-bidentate ligand. This hypothesis was confirmed by NOE NMR spectroscopy that suggested a different structure for the Cu complex of the alcohol ligand relative to the methylether and the dimethylamino ligands, which could explain the observed stereochemical inversion. 

Fig. 7.4. Tricyclic transition structures for aminoalcohol catalysts syn and anti refer to the relationship between the transferring group and the bidentate ligand cis and trans refer to the relationship between the aldehyde substituent and the coordinating zinc. Reproduced from J. Am. Chem. Soc., 125, 5130 (2003), by permission of the American Chemical Society.

The structures of [TpMe2]2Zn (80) and [Tpph]2Zn (85) have been determined by x-ray diffraction (Fig. 28). Interestingly, [TpMe2]2Zn and [TpPh]2Zn do not possess similar structures. Specifically, whereas the zinc center in [TpMe2]2Zn is six-coordinate and octahedral, the zinc center in [TpPh]2Zn is only four-coordinate and tetrahedral. Thus, the potentially tridentate [TpPh] ligand acts only as a bidentate ligand in [i72-TpPh]2Zn. However, it should be noted that the Fe in the related complex [TpPh]2Fe is octahedrally coordinated (90). 

Triphenylformazan behaves as a bidentate ligand forming 2 1 complexes (217) with divalent copper, nickel, and cobalt.377 Formazan metal complexes can be compared to complexes of azo dyes or beta diketones due to structural similarity.301,302 In general, formazan metal complexes have low stability toward acids. However, when electron-donating substituents are added to the aromatic ring, a considerable enhancement in stability is observed. Cationic complexes of type 218 are also known. The complexation of formazan with metal cation can be accompanied by oxidation to the tetrazolium salt and the formation of a complex... 

A review8 with more than 186 references discusses the synthesis of Rh and Pd complexes with optically active P,N-bidentate ligands and their applications in homogeneous asymmetric catalysis. The effect of the nature of the P,N-bidentate compounds on the structure of the metal complexes and on enantioselectivity in catalysis was examined. Allylic substitution, cross-coup-ling, hydroboration and hydrosilylation catalyzed by Rh or Pd complexes with optically active P,N-bidentate ligands are considered. 

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