Divalent nickel, cobalt and copper complexes of tetradentate macrocycle, dibenzo (f, n) 2, 4, 10, 12- tetramethyl-1, 5, 9, 13-tetrazacyclohexadeca [16] 1, 3, 9, 11-tetraene

doi:10.1016/S0277-5387(00)80823-2

Polyhedron

Volume 1, Issue 4, 1982, Pages 377-381

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Abstract

Metaphenylenediamine and acetylacetone react in presence of divalent nickel, cobalt and copper salts to form complexes of a 16-membered N₄ tetradentate macrocycle, dibenzo-(f,n)-2, 4, 10, 12-tetramethyl-1, 5, 9, 13-tetrazacyclohexadeca-[16]-1, 3, 9, 11-tetraene. The complexes are characterised to be distorted octahedral of the type [M(Me₄[16] 1, 3, 9, 11-tetraene N₄)X₂] where M = Ni(II), Co(II) and Cu(II); X = Cl, Br, NO₃ or NCS. The ligand coordinates through azomethine or imine nitrogen atoms which are bridged by acetylacetone moieties. The electrical conductance, molecular weight, magnetic, electronic and IR spectra are discussed.

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Template engineered biopotent macrocyclic complexes involving furan moiety: Molecular modeling and molecular docking
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The lower value of v(CN) in the complexes may be explained on the basis of drift of the lone pair electron density from the heteroatom (nitrogen) toward the central metal atom [21] indicating that coordination occurred through the nitrogen of the CN. The bands in the region 440–470 cm−1 may corresponds to v(MN) vibrations and the bands in the range 220–250 cm−1 v(MO) [22]. The presence of (MN) band in all the complexes identifies coordination of the azomethine nitrogen [23].
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The electronic spectral data of the complexes in the solution state (in DMSO) were recorded within 200–1100 nm. The magnetic moment value in the range 3.90–4.00 B.M. at room temperature for Cobalt complexes corresponds to the presence of three unpaired electrons [25]. The electronic spectra of cobalt complexes showed bands at ∼940–970 (v1), 510–550 (v2) and 370–395 nm (v3) [25] corresponding to 4T1g → 4T2g (F), (v1); 4T1g → 4A2g (F), (v2) and 4T1g (F) → 4T1g (P), (v3); respectively.
A new mixed thia-aza macrocyclic complexes with Schiff base viz. 15-thia-3,4,9,10-tetraazabicyclo[10.2.1]pentadeca-1(14),2,10,12-tetraene-5,8-dione containing transition metals, M = Co(II), Ni(II), Cu(II) and Zn(II) and X = Cl⁻, NO₃⁻, OAc⁻, has been synthesized, resulting in the final constitution of 1:1:1 M ratio, by the condensation of succinyldihydrazide and thiophenedicarboxaldehyde. The metal complexes have been investigated with the help of various physico-chemical techniques viz. elemental analyses, magnetic susceptibility, thermal, conductivity measurements, spectral (IR, UV, ESR, NMR and mass) and X-ray diffraction techniques. The low value of molar conductivity indicates the non-electrolytic nature of the complexes and a distorted octahedral geometry has been proposed on the basis of various physico-chemical studies. X-ray diffraction indicates the presence of monoclinic crystal system. The complexes have been investigated for in vitro antibacterial, antifungal and antioxidant activity. All the complexes show moderate to significant activity.
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Four bacteria, S. aureus (MTCC 96), B. subtilis (MTCC 121) (Gram positive), E. coli (MTCC 1652) and P. aeruginosa (MTCC 741) (Gram negative) were used in the present study. The antibacterial activities of newly synthesized macrocyclic metal complexes were evaluated by the agar well diffusion method [34]. All the microbial cultures were adjusted to 0.5 McFarland standards, which is visually comparable to a microbial suspension of approximately 1.5 × 108 cfu/ml [35].
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Divalent nickel, cobalt and copper complexes of tetradentate macrocycle, dibenzo (f, n) 2, 4, 10, 12- tetramethyl-1, 5, 9, 13-tetrazacyclohexadeca [16] 1, 3, 9, 11-tetraene

Abstract

Coord. Chem. Rev.

Spectrochim Acta

J. Inorg. Nucl. Chem.

Record. Chem. Progr.

Z. Chem.

Z. Anorg. Allg. Chem.

J. Am. Chem. Soc.

Ind. J. Chem.

Transition Met. Chem.

Proc. XX. I.C.C.C. Inorg III