CONTENTS
Chapter 4 Chapter 4 (Part B): Inclusion of Aldehyde or Oxime in Cadmium Coordination Polymer and Conversion of Aldehyde to Oxime
1.13: Coordination chemistry of oxime derivatives
The oximes show amphiprotic behavior due to acidic hydroxyl group and basic nitrogen atom present on them. Oximes have played a crucial role in the development of coordination chemistry.110 In early examples of coordination chemistry of oximes, dimethylglyoxime was identified as a strong binding ligand to nickel(II) ion forming stable bis-dimethylglyoximato nickel(II)complex.111 Oxime or oximato groups can bind to a metal ion in different ways110; some of the common binding modes of oxime or oximato groups with a metal ion are shown in Fig. 1.27.
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Figure 1.27: Coordination modes of oxime or oximato groups with metal ion.
Phenolic oximes (1.61-1.63) are used extensively in industry for metal extraction from waste streams, mainly for the extraction of copper.112 They show remarkable selectivity for copper(II) over other metal ions present in solutions together with copper ions. The favorable selectivity for copper is due to the fitting of copper ion in the space formed by two hydrogen bonded ligands as 1.61a, shown in Fig. 1.28. Another important feature of phenolic oximes is their ability to form polynuclear complexes as both the oximate and phenolate groups can bridge metals.
Figure 1.28: Some oxime ligands (1.61-1.67) and 1.61a is a copper(II) complex with 1.61.
Phenolic oximes 1.61 or 1.62 on double deprotonation behave as tridentate bi-nucleating ligands, which may be coordinated to the metal ions by nitrogen or oxygen atoms participating in the formation of the metallacrown ring. There are plenty of examples on polynuclear trivalent metal complexes with oxime 1.61 or 1.62 as ligands with Fe(III)113 or Mn(III).114 Majority of the polynuclear oxime complex reports include dinuclear,113a trinuclear,114 tetranuclear,115 hexanuclear116 having azide,117 halide,116 perchlorate,114b and carboxylate115 counterions or co-ligands.
Both compounds 1.61 and 1.62 form metal complexes with transitions metal ion like nickel.118 Hexanuclear complexes of manganese and iron metal ions with 1.61 and 1.62 oxime ligands have shown (Fig. 1.29) single-molecule magnet property. Salicylaldoxime- based [MnIII6] complexes with general formula [MnIII6O2(O2CR)2(1.61)6(EtOH)4] are prepared from reaction of manganese acetate dihydrate
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and salicylaldoxime (1.61) in ethanol.119 The metallic core of manganese complex consists of two off-set, stacked [MnIII3(µ3-O)(1.612-)3]+ triangles where each edge of the triangle is bridged by one oximate -N-O- group; thus, creating an oxo-centred {Mn-N-O-}3 ring.
Magnetic studies revealed S=4 ground states with axial anisotropies of the order D = -1.2 cm-
1 and ‘‘moderate’’ energy barriers to magnetization reversal of Ueff = 28 K. Hexanuclear iron complex of oxime 1.62 with the general formula [Fe6O2(OH)2(Et-sao)2(Et-saoH)2(O2CPh)6] shown in Fig. 1.29b also showed single-molecule magnets property like the hexanuclear manganese complex (Fig. 1.29a).120
(a) (b)
Figure 1.29: Hexnuclear (a) manganese(III) and (b) iron(III) complexes of 1.61 and 1.62 oximes respectively.
Compound 1.63a formed octametallic Cu(II) wheels on simple reaction with copper(II) salts, and also it formed single-stranded hexametallic mixed-metal Na2Cu4 wheel.121 Octametallic Cu(II) wheels and hexametallic mixed-metal Na2Cu4 wheel of compound 1.63a is the first examples of metalo-wheels of this compound. Similarly compound 1.63b formed dodecametallic Mn(III) wheel,122 and heterometallic complexes with Zn(II) and Ln(III) metal ions.123 Phenolic oxime based ligand 3-methyloxysalicylaldoxime 1.64 is useful to construct 3d/4f heterometallic clusters. From this ligand a family of novel heptanuclear [Mn3Ln4] metal complexes was obtained and structurally characterized which are represented examples of 3d/4f clusters.124
Powell and her co-workers have reported heteromettallic complexes of 1.64 with transition and lanthanide metal ions with interesting magnetic properties.125 3-Dialkylaminomethyl substituted salicylaldoxime (1.65) are used as an efficient metal salt extractant. Compound 1.65 forms a zwitterionic complex with copper(II) and zinc(II) metal salts, where some anions like nitrate, tetrafluoroborate and trifluoroacetate are found in outer sphere of the complex.126 But with halides such as chloride or bromide it formed inner coordinated metal
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complex, leading to high chloride selectivity and very good mass transport efficiencies of copper(II) chloride.
2-Hydroxy-1-naphthaldehyde oxime (1.66) forms binuclear metal complex with manganese(III) having general formula [MnIII2(1.662-)2(1.66-)2(MeOH)2].4MeOH.127 And also it forms hexanuclear manganese complex in presence of naphthalene-1,8-dicarboxylic acid as a co-ligand.128 Benzoin oxime 1.67 is used to prepare family of decanuclear copper(II),129 nickel(II)130 and manganese (III)131 complexes, each showing anti- ferromagnetic property. Phenolic oxime ligands form different transitions metal complexes having various nuclearity are well described by Tasker and co-workers,132 where ‘‘metal oximate’’ building blocks are used as ligands to synthesize various homo and heterometallic paramagnetic complexes. However in coordination chemistry, pyridyl oximes has significant role to synthesized transition metal oxime or metal-oximate complexes with various nuclearity. Pyridyl oximes (1.68-1.70; R= H, Me, Ph) have significance in synthesise of polynuclear transition metal oxime or metal-oximate complexes (Fig. 1.30). The first structurally characterized metal complex of pyridine-2-carbaldehyde oxime was {Cu3(OH)(SO4)-(1.68)3}.133 The dianionic species generated from 1.68-1.70 are important as chelating and bridging (μ2-μ4) agents.134 Compounds 1.68-1.70 form dodecanuclear and hexadecanuclear Ni-cluster on simple reaction with NiCl2.6H2O in presence of base.135
Figure 1.30: Some heterocyclic oxime derivatives are used as ligands for synthesis of metal complexes.
Methyl 2-pyridyl ketone oxime (1.69) forms heterometallic complexes with zinc(II) and lanthanide(III) ions such as [ZnLn(1.69-)3(1.69)3]-(ClO4)2 or [ZnLn(NO3)2(1.69-)3(1.69)].
These blue-green complexes show ligand-based photo-luminescence.136 The compound 1.71 is a potential flexidentate pyridyl-azo-oxime, it provides a series of homoleptic complexes [CoIII(L1-)3] or [CoIII(L1-)2]ClO4. These complexes have N6 and N4O2 coordination environments respectively.137 Ligand 1.72, has similar structural feature as that of 2-pyridyl oxime, but coordination chemistry of this ligand 1.72 is very limited. It provides example of
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supramolecular assembly when complexes to ions like silver (I) or copper(I). The crystal structure of [Ag(1.72)2](PF6) contains cations that is comprised of two ligands coordinated through the 3-pyridyl nitrogen atoms to one silver(I) ion.138 In this complex the oxime moieties are cis with respect to each other, and cations are linked by complementary O-H···N hydrogen bonds that are formed between oxime moieties present on neighboring ligands.
These interactions generate an infinite 1D chain like assembly. In crystal lattice, the adjacent chains are linked by C-H···O hydrogen bonds. But in the crystal structure of [CuI(1.72)]n each tetrahedral copper(I) ion is coordinated to three µ3-I- ligands to generate an infinite one- dimensional assembly. Porous molecular materials are formed as a consequence of oxime 1.73 coordinating to nickel(II) metal ion.139
Figure 1.31: one-dimensional tape-like structure of copper(II) adipate complex with 1.73.
Metal complexes of oxime ligand 1.73 with zinc(II) and cadmium(II) show nonlinear optical (NLO) properties.140 Polymeric luminescent zinc(II) and cadmium(II) metal aliphatic dicarboxylate complexes of 1.72 or 1.73 with are useful for gas adsorption.141 The soft nature of 1D coordination polymer crystals of copper(II) adipate complex of 1.73 (Fig. 1.31) was investigated by nano-indentation study for mechanical stress in conditions of different indentation loading.142 Some of the polynuclear metal complexes of ligand 1.74 show single- molecular magnet proerties.143 Ligand 1.74 forms nano-dimensional octadecanuclear heterometallic {Cu6Ln12} clusters with assistance of bridging N3-
Ligands. Depending on the 4f-metal ion present in these octadecanuclear complexes some of them shows single- molecule magnetic behavior with large magnetic entropy changes.144
Dimeric uranium complex of 1.74 [UO2(1.74)Cl]2 is stable in solution as shown by ESI-MS spectrometry and NMR spectroscopy.145 Ligand 1.74 forms palladium(II) and platinum(II) chelate complexes, which shows biological activity.146 Pyrazine-2-amidoxime (1.75) is another ligand having similarity to oxime 1.68. This ligand has an extra metal binding site to form metal complexes with 3d-4f metal ions. It forms decanuclear {Dy4Ni6} cluster with a central butterfly-shaped {Dy4(μ3-OH)2} core and six peripheral diamagnetic nickel(II) ions.147 Different nuclearities metal complexes of nickel(II) or cobalt(II/III) metal ions are formed by indeno-quinoxaline ligand 1.76 (Fig.1.30), in such complexes nuclearities ranges
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from 3 up to 8.These complexes have shown interesting magnetic properties.148 The reaction of 8-quinolinol-2-carboaldoxime (1.77) with nickel(II) and lanthanum(III) metal salts afforded different heterometallic decanuclear metal complexes and magnetic studies on these complexes reveal an overall anti-ferromagnetic behavior.149
The foregoing discussions have suggested that the oxime functional group or oxime together with other functional group is used as ligands for making of metal complexes with different nuclearity. The special interests on oxime complexes because of single molecular magnetic properties and unusual optical properties associated with many clusters. Porous materials can be also successfully generated from complexation of oxime with metal ions and such complexes are useful for gas adsorption study. However, many of metal complexes are sensitive to cations or anions; hence leave huge scopes to use oxime based molecules to explore interesting properties.