Tetradentate chelators

Bp2pyr, in which each pyrazolyl ring is functionalized with a pyrazin-2-yl group at the C2 position, is a potentially chelating tetradentate ligand with two externally directed N atoms available for additional... 

Cu, Ni, Pd, V GC-MIP-OES metal chelates tetradentate -ketoamine SchifF bases, range 6-23 pg of metal [532]... 

Eig. 1. Types of chelates where (1) represents a tetracoordinate metal having the bidentate chelant ethylenediamine and monodentate water (2), a hexacoordinate metal bound to two diethylenetriamines, tridentate chelants (3), a hexacoordinate metal having triethylenetetramine, a tetradentate chelant, and monodentate water and (4), a porphine chelate. The dashed lines iadicate coordinate bonds. 

The P-N chelate (91) (dapdmp) exhibits a variety of coordination geometries in complexes with divalent Co. Pseudotetrahedral Co(dapdmp)X2 (X = C1, Br, I, NCS), low-spin five-coordinate [Co(dapdmp)2X]+ (X = C1, Br, I), planar [Co(dapdmp)2]2+ and pseudo-octahedral Co(dapdmp) (N03)2 were all identified.390 The tetradentate P2N2 Schiff base complex (92) is formed by reacting the free ligand with CoI2. The iodo complex is low spin and square pyramidal.391... 

The novel tetrabasic ligand l,3-bis(5-methylpyrazole-3-carboxamido)propane forms a trinuc-lear Co111 Co11 Co111 complex (196). The tetradentate diamide-pyrazolyl chelates encircle the terminal trivalent metal ions while the central divalent Co is in a distorted tetrahedral environment provided by the four bridging pyrazolyl rings.881... 

As a part of their work on copper(I)-dioxygen chemistry, Schindler and co-workers220 synthesized copper(I) (Section 6.6.4.2.2(iv)) and copper(II) complexes ((235) r = 0.12, and (236) r = 0.08) of a few tetradentate ligands, varying in their flexibility due to the presence of different chelate ring-forming arms, and studied their redox properties. Karlin and co-workers observed a... 

Investigation of the coordination of tetradentate N2S2 ligands has been reported for gallium and indium.79 This type of chelate had previously been incorporated into many technetium complexes for biomedical applications. 

Another factor that relates complex stability and siderophore architecture is the chelate effect. The chelate effect is represented by an increase in complex stability for a multidentate ligand when compared to complexes with homologous donor atoms of lower denticity. The effect can be observed when comparing the stability of complexes of mono-hydroxamate ligands to their tris-hydroxamate analogs, such as ferrichrome (6) or desferrioxamine B (4). However, the increase in stability alone is not sufficient to explain the preponderance of hexadentate siderophores over tetradentate or bidentate siderophores in nature, and the chelate effect is not observed to a great extent in some siderophore structures (10,22,50,51). 

Complexes formed by tetradentate siderophores involve stepwise complex formation and therefore, have somewhat different equilibria from their hexadentate analogs. Initial chelation will occur with a tetracoordinate FeL complex forming. A subsequent equilibrium then occurs, where the FeL complexes will react in a 2 1 stoichiometry with free ligands in solution to form a single Fe2L3 complex (coordinated water and charges not shown for clarity). 

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