Cobalt(II) and copper(II) assembling through a functionalized oxamate-type ligand

Oliveira, Thiago Levi Silva; Kalinke, Lucas H. G.; Mascarenhas, Eric J; Castro, Ricardo A. E.; Martins, Felipe Terra; Sabino, José R.; Stumpf, Humberto O.; Ferrando, J. C.; Julve, Miguel; Lloret, Francesc; Cangussu, Danielle

doi:10.1016/j.poly.2014.05.051

Cited by 12 publications

(15 citation statements)

References 57 publications

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“…Analyzing the Cambridge Structural Database (CSD version 5.39, May 2018), 71 only three coordination compounds with those features were found. 39,72 Among these, two of them were reported by our research group, which show the MeHpcpa − and Hpcpa 2− ligands (CCDC refcode: VOPLIX and VOQDEM, respectively). 39 The other one contains two oxamate bridges and only one deprotonated carboxylic acid, which changed therefore the geometry of the final complex and led to an entirely different packing due to a further coordination to an alkaline metal.…”

Section: Description Of the Structuresmentioning

confidence: 98%

“…39,72 Among these, two of them were reported by our research group, which show the MeHpcpa − and Hpcpa 2− ligands (CCDC refcode: VOPLIX and VOQDEM, respectively). 39 The other one contains two oxamate bridges and only one deprotonated carboxylic acid, which changed therefore the geometry of the final complex and led to an entirely different packing due to a further coordination to an alkaline metal. 72 Moreover, all these three structures contain the protonated carboxylic acid, as observed in 1.…”

Section: Description Of the Structuresmentioning

confidence: 98%

“…Among all other structures with only the Hpcpa 2− ligand, which were reported by some of us, it was also verified the formation of both a coordination polymer and a dimer, indicating the versatility of the Hpcpa 2− ligand to output complexes with different dimensionality. 39 Crystal structures of coordination compound with carboxylic acid allied to an oxamate bridge as ligands are limited in the literature. Analyzing the Cambridge Structural Database (CSD version 5.39, May 2018), 71 only three coordination compounds with those features were found.…”

Section: Description Of the Structuresmentioning

confidence: 99%

“…The presence of this acid hydrogen limited the formation of a coordination polymer, which results in an isolated coordination compound, as mentioned. Meanwhile, structures 2 and 3 are isostructural between each other and to VOQDEM, 39 which has the formula {[Co(Hpcpa)(…”

Section: Description Of the Structuresmentioning

confidence: 99%

“…The first attempts yielded the cobalt(II) chain of formula {[Co(Hpcpa)(H 2 O) 3 ] n • 3/2nH 2 O} and the dicopper(II) complex [Cu 2 (MeHpcpa) 4 (MeOH) 2 ] (MeHpcpa − = monoanion of the methyl ester derivative of the H 3 pcpa). 39 The Hpcpa 2− ligand exhibits a bidentate/monodentate bridging mode in the former compound whereas only the carboxylate group in the syn-syn bridging mode of the MeHpcpa − ligand is involved in the second one, the monoprotonated methyl oxamate fragment remaining uncoordinated. As an extension of this work, we present here the synthesis and X-ray structures of the compounds of formula…”

Section: Introductionmentioning

confidence: 99%

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New Metal-Organic Systems with a Functionalized Oxamate-Type Ligand and MnII, FeII, CuII and ZnI

Maciel

Kalinke

Valdo

et al. 2019

J. Braz. Chem. Soc.

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Four new complexes of formula [Fe(H 2 pcpa) 2 (H 2 O) 2 ] (1), {[Mn(Hpcpa)(H 2 O) 3 ]•1/2H 2 O} n (2), {[Zn(Hpcpa)(H 2 O) 3 ]•1/2H 2 O} n (3) and [Cu 2 (Hpcpa) 2 (bipy) 2 ]•8H 2 O (4) [H 3 pcpa = N-(4-carboxyphenyl) oxamic acid; bipy = 2,2′-bipyridine] have been synthesized and their structures determined by X-ray diffraction. The structure of 1 consists of mononuclear iron(II) units where each iron(II) ion is six-coordinate by two trans-positioned water molecules and two bidentate H 2 pcpa − ligands building a distorted octahedral environment. 2 and 3 consist of neutral zigzag chains of Mn II and Zn II ions respectively, the Hpcpa 2− groups acting as linkers in a bidentate/monodentate coordination mode with three mer-positioned water molecules achieving the six-coordination around the metal centers. Compound 4 is a neutral centrosymmetric dicopper(II) complex where two Hpcpa 2− groups adopting the bidentate/monodentate coordination mode and act as bridges and bidentate bipy molecules act as end-cap ligands, describing a square pyramidal surrounding around each copper atom. Cryomagnetic measurements for 1, 2 and 4 in the temperature range 1.9-300 K reveal the occurrence of a field-induced single-ion magnet (SIM) behavior (1) and weak interchain (J =-0.22 cm-1 , 2) and intradimer (J =-0.39 cm-1 , 4) antiferromagnetic interactions, the Hamiltonian being defined as H =-J S a. S b .

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Section: Description Of the Structuresmentioning

confidence: 98%

Section: Description Of the Structuresmentioning

confidence: 98%

Section: Description Of the Structuresmentioning

confidence: 99%

Section: Description Of the Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

New Metal-Organic Systems with a Functionalized Oxamate-Type Ligand and MnII, FeII, CuII and ZnI

Maciel

Kalinke

Valdo

et al. 2019

J. Braz. Chem. Soc.

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Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

et al. 2019

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Trinuclear Co II and Ni II complexes have been assembled using an octadentate Mannich-Schiff-base proligand H 2 L 2 which is obtained by reacting the Mannich base HL 1 with propylenediamine (2:1 molar ratio). HL 1 is obtained from 5bromo-salicylaldehyde and N,N,N′-trimethyl-ethylenediamine. The reaction of H 2 L 2 with nickel(II) and cobalt(II) as nitrate salts affords the trinuclear complexes [Ni 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (1) and [Co 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (2) in which the metal ions are bridged by one phenoxido and a nitrato-oxygen atoms. Within each complex, two of the four nitrato groups act as chelating ligands against the terminal metal ions. The central metal ions in 1 and 3 ) 2 ]· 2CH 3 CN (5). The magnetic properties of the five compounds have been investigated, revealing the occurrence on intramolecular antiferro-(1 and 2) and ferromagnetic interactions (3, 4 and 5). The nature and size of these interactions are discussed and compared to previously reported results on related systems.Scheme 1. Macrocyclic (A) and end-off (B) compartmental proligands nation environments. Such complexes have relevance in molecular magnetism, [3] biomimetic inorganic chemistry, [4] and catalysis. [5] Using 5-substituted salicylaldehydes as a platform for Mannich and Schiff reactions, the sizes of the two compartments can be tuned by choosing amine precursors with various Scheme 2. Dissymmetric proligands Full Paper numbers of carbon atoms. Moreover, the two amines can contain additional coordinating groups. Other proligands obtained following this strategy are potentially tetradentate and contain only one compartment, Mannich or Schiff (see Scheme 2). These organic molecules can generate not only binuclear complexes, but also high nuclearity clusters. [6] In this paper we report on new trinuclear complexes which are aggregated using an octadentate Schiff-Mannich base ligand featuring a salen-like moiety. Their syntheses, crystal structures and magnetic properties are discussed. Results and DiscussionThe new ligand has been obtained starting from 5-bromosalicylaldehyde: in the first step, the Mannich reaction leads to the intermediate HL 1 species (see Scheme 3); [7] in the second step, the octadentate ligand H 2 L 2 is obtained by reacting HL 1 with propylenediamine (2:1 molar ratio). This last reaction occurs in situ, in the presence of transition metal ions. The H 2 L 2 proligand combines the rigid salen-like coordinating moiety with the flexible Mannich arms, each one with two nitrogen atoms. We have tested its coordination behavior in the reaction with nickel(II) and cobalt(II) as nitrate salts. In both cases, trinuclear complexes of formula [Ni 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (1) and [Co 3 (L 2 )(NO 3 ) 4 ]·CH 3 CN (2) have been assembled.Two nitrato ligands are chelated to the two peripheral metal ions and the other two act as monoatomic bridges. By reacting these compounds with NaN 3 and NaNCS, the bridging nitrato groups have been replaced by Figure 1. (a) Perspective view of the trinuclear complex 2. (b) Det...

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A Bis‐Polydentate Oxamate‐Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain

Chamoreau

et al. 2020

Eur J Inorg Chem

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The reaction of the N‐(2‐hydroxyphenyl)oxamate ligand (ohpma) has been investigated with cobalt(II) and copper(II) ions. It has led to two coordination compounds, (TMA)3[{CoIII(ohpma)2CoII(MeOH)2}3]·10H2O·5MeOH (1) and (HNEt3)[Cu(ohpma)] (2). Both compounds have been characterized by single‐crystal X‐ray diffraction and magnetometry. The X‐ray diffraction studies have revealed atypical structures that are not commonly observed in oxamate coordination chemistry with a macrocyclic arrangement for the mixed‐valence cobalt‐based complex 1, and a helical chiral chain for compound 2. In the latter, the bis‐polydentate nature of the (ohpma)3– ligand with distinct tridentate and bidentate coordination sites creates a chirogenic center on the copper ion. The investigation of the magnetic properties shows for complex 1 a single‐molecule magnet behavior detectable under static field, while antiferromagnetic interactions dominate the behavior of 2.

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Cobalt(II) and copper(II) assembling through a functionalized oxamate-type ligand

Cited by 12 publications

References 57 publications

New Metal-Organic Systems with a Functionalized Oxamate-Type Ligand and MnII, FeII, CuII and ZnI

New Metal-Organic Systems with a Functionalized Oxamate-Type Ligand and MnII, FeII, CuII and ZnI

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

A Bis‐Polydentate Oxamate‐Based Achiral Ligand That Can Stabilize a Macrocyclic Mixed Valence Compound or Induce a 1D Helical Chain

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