skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide

Abstract

Nickel(II) complex have been synthesized by treating a 14-membered ring tetraaza macrocyclic compound, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium, bromide (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} with nickel acetate in metanol. The complex was characterized using elemental analysis, Fourier Transform Infrared (FTIR), Ultraviolet-Visible (UV-Vis), and single crystal diffraction (X-ray). The nickel atom coordinates through four nitrogen atoms in the ligand. Square planar geometry has been proposed for this complex.

Authors:
; ; ;  [1]
  1. School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)
Publication Date:
OSTI Identifier:
22308329
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 1614; Journal Issue: 1; Conference: 2014 UKM FST postgraduate colloquium, Selangor (Malaysia), 9-11 Apr 2014; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACETATES; ATOMS; BROMIDES; BROMINE; FOURIER ANALYSIS; FOURIER TRANSFORMATION; HYDROGEN 4; INFRARED SPECTRA; MONOCRYSTALS; NICKEL; ULTRAVIOLET RADIATION; X-RAY DIFFRACTION

Citation Formats

Yusoff, Latifah M., Yusoff, Siti Fairus M., Ismail, Wafiuddin, and Yamin, Bohari M. Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide. United States: N. p., 2014. Web. doi:10.1063/1.4895222.
Yusoff, Latifah M., Yusoff, Siti Fairus M., Ismail, Wafiuddin, & Yamin, Bohari M. Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide. United States. doi:10.1063/1.4895222.
Yusoff, Latifah M., Yusoff, Siti Fairus M., Ismail, Wafiuddin, and Yamin, Bohari M. Wed . "Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide". United States. doi:10.1063/1.4895222.
@article{osti_22308329,
title = {Synthesis and characterization of Ni(II) complex with 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium bromide},
author = {Yusoff, Latifah M. and Yusoff, Siti Fairus M. and Ismail, Wafiuddin and Yamin, Bohari M.},
abstractNote = {Nickel(II) complex have been synthesized by treating a 14-membered ring tetraaza macrocyclic compound, 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7,14-dienium, bromide (Me{sub 6}N{sub 4}H{sub 4})Br{sub 2} with nickel acetate in metanol. The complex was characterized using elemental analysis, Fourier Transform Infrared (FTIR), Ultraviolet-Visible (UV-Vis), and single crystal diffraction (X-ray). The nickel atom coordinates through four nitrogen atoms in the ligand. Square planar geometry has been proposed for this complex.},
doi = {10.1063/1.4895222},
journal = {AIP Conference Proceedings},
number = 1,
volume = 1614,
place = {United States},
year = {Wed Sep 03 00:00:00 EDT 2014},
month = {Wed Sep 03 00:00:00 EDT 2014}
}
  • Two isomers of the square-planar nickel(II) complex of 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradecane (HTIM) were prepared from the nickel (II) complex of 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8-10-tetraene (TIM) by NaBH{sub 4} reduction in aqueous solution. The properties of Ni(II) complexes, Ni(I) complexes, and Ni(I)-CO complexes with a series of 14-membered macrocyclic N{sub 4} ligands were studied by means of UV-vis, NMR, and IR spectroscopy. The CO binding constants range from 1.3 x 10{sup 2} to 2.8 x 10{sup 5} M{sup -1} at 25 {degrees}C in acetonitrile. The crystal structures of C-RSSR-[Ni{sup I}HTIM]ClO{sub 4} (1), C-RSSR-[Ni{sup II}HTIM](ClO{sub 4}){sub 2} (2), C-RRSS-[Ni{sup II}HTIM](ClO{sub 4}){sub 2} (3) and [Ni{sup II}TIM](ClO{sub 4}){submore » 2} (4) have been determined from single-crystal X-ray diffraction data collected by using Mo K{alpha} radiation. All complexes have square-planar geometry and the stereochemistry of the four coordinating N atoms in complexes (1), (2), and (3) is Trans III. Although the two sets of Ni-N distances of 2.083(3) and 2.053(3) {angstrom} for the Ni(I) complex, (1), are much longer than those of 1.969(1) and 1.969(1) and 1.948(2) {angstrom} for the corresponding Ni(II) complex, (2), distortion of the macrocycle core was not observed upon the reduction of the metal center. The structural changes associated with the reduction of Ni(II) to Ni(I) in square-planar complexes can be classified in three ways: (1) expansion of Ni-N distances; (2) distortion of nickel core; (3) both expansion and distortion.« less
  • Equatorial coordination of L (L=5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) to the metal center of cobalt has been previously reported as resulting in two diastereomers, one racemic and one meso. Using the same general procedure as previously reported, the authors report the production of a product whose spectral properties do not agree with either the meso or the primary racemic isomer. Results of single-crystal x-ray diffraction studies indicate that the product of the reaction is the third possible geometric isomer, the secondary racemic complex. The structure and properties of the complex are reported.
  • The authors have determined the crystal structure of the compound ((CuL)I)I x 2.5H2O where L is C16H32N4, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradeca-4,11-diene (Syntex P21 automatic diffractometer, Mo K radiation, 3700 measured I/sub hk ell/ of which 2600 greater than or equal to 2sigma/sub I/, Theta/2 Theta scanning, 3 less than or equal to 2 theta less than or equal to 47). The metric of the unit cell is: a = 7.702(2), b = 20.755(8), c = 17.295(6) A, US = 115.09(2), V = 2504(1) AT, d/sub calc/ = 1.71 g/cmT, Z = 4, space group P21/C. The structure is of the island type. Themore » nearest environment of the Cu atom consists of four N macrocyclic ligands with mean Cu-N distance 1.99 A, forming an almost plane square. The two independent I anions are also crystallochemically different: they make up the coordination of the Cu atom to pyramidal (coordination number 4 + 1, Cu-I, 3.031 A), forming a cation of the composition ((CuL)I) . The second I is an anion and together with H2O molecules lies between these complex cations. The H2O molecules are joined by hydrogen bonds.« less
  • The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL{sup +} with CO{sub 2} and with CO and isolated as a perchlorate salt: IR (Nujol){nu}{sub CO} 1916 cm{sup {minus}1}; UV-vis (CH{sub 3}CH, {lambda}{sub max} ({epsilon})) 310 nm (3900 M{sup {minus}1} cm{sup {minus}1}), 430 sh (770), 510 sh (360), 1040 (240). In CH{sub 3}CN solvent its stability constant is {approx} 3 {times} 10{sup 8} M{sup {minus}1} at 25{degree}C. Structures of the square-pyramidal carbonyl complex and two other complexes of the title macrocycle have been determined from single-crystal x-ray diffraction data collected with use of Momore » K{alpha} radiation. Crystallographic data: (CoL(CO))(ClO{sub 4}) (1), C2, a = 15.362 (3) {angstrom}, b = 7.580 (5) {angstrom}, c = 9.611 (3) {angstrom}, {beta} = 108.91 (2){degree}, V = 1059 (1) {angstrom}{sup 3}, Z = 2 (R = 0.057, R{sub w} = 0.069); N-meso,trans-CoLCl{sub 2} (2), Pbca, a = 11.570 (3) {angstrom}, b = 12.695 (3) {angstrom}, c = 13.309 (2) {angstrom}, V = 1954 (1) {angstrom}{sup 3}, Z = 4 (R = 0.075, R{sub w} = 0.070); cis-(CoL(CO{sub 3}))ClO{sub 4} (3), C2, a = 15.072 (5) {angstrom}, b = 7.603 (4) {angstrom}, c = 9.703 (3) {angstrom}, {beta} = 109.74 (3){degree}, V = 1047 (1) {angstrom}{sup 3}, Z = 2 (R = 0.033, R{sub w} = 0.048). The three structures contain square-pyramidal, five-coordinate cobalt(I) (1), strongly axially distorted six-coordinate cobalt(II) (2), and six-coordinate cobalt(III) with L occupying cis-coordination positions (3). They thus provide a striking illustration of the adaptability of L to a variety of coordination numbers and oxidation states. 30 refs., 3 figs., 8 tabs.« less
  • The complexation of nickel acetate with tetraaza involves deprotonation of protonated amine nitrogen to form neutral ligand coordinated to the nickel via the four nitrogen atom. The dication complex is paired with thiocyanate anions. The complex was characterized by elemental analysis, UV-VIS and FTIR spectroscopic method. The crystal structure of nickel complex characterized by X-Ray crystallography and adopts square planar geometry.