Islamic Azad University- Karaj Branch Faculty of Science Department of Chemistry Subject: Synthesis, Separation and Spectroscopic and Structural study on 1,3-bis(2-methoxyphenyl)triazene & 1,3-bis(2-methoxyphenyl)triazene as Ligand and their Complex with Hg cations Thesis advisor: Mohammad R. Melardi; Ph.D. Consulting advisor: Mohammad K. Rofouei; Ph.D. By: Mohammad Barkhi

Triazenes Triazenes are a class of organic compounds characterized by the presence of diazoamino functional group (NNN). The simplest member of the family is known just as Triazene. These compounds have been used in a variety of application; in transition metal complexes as ligand (in Triazenide form), in polymer synthesis and anticancer drugs. J. Am. Chem. Soc Inorg. Chem. 2005

Application of Triazenes In medicine Poisonous Cations & Anions such as Mercury, Cadmium, Cyanide,... Separation from environment (J. Org. Chem. 2006: Analytica Chimica Acta 2005) Pharmacological Research (2007) In food & cosmetics industries as dye (11 th report on carcinogens) DacarbazineTemozolomide

Polymer & Laser industries Triazene polymers revealed superior properties for applications in the near-IR which could be used as a thruster for micro satellites. (J. Photochem. Photobio. A 2001) Complexation with metal cations Triazenes can act as ligand in metal complexes. There are many report in this field.

Properties of triazene ligand with Aryl groups as 1,3-substituents (ArNNNHAr) have been intensely studied during the past years. The simplest Aryltriazene is 1,3- diphenyltriazne (Hdpt).

Preparation methods There are several methods to preparation Aryltriazenes: 1. By the action of sodium nitrite on aniline (routine method) (1937). 2. By the action of ammonium nitrate and hydrogen sulfide on aniline hydrochloride in the presence of iron(1913). 3. By the action of silver nitrite on aniline hydrochloride(1897). 4. Diazotization of aniline, aniline hydrochloride, and aniline sulfate with sodium nitrite and silver nitrite(1897).

The coordination properties of 1,3-diphenyltriazene was found to be: N 1 -monodentate ligand Trans-Pd[3-(2-flurophenil)-1-(4-nitrophenil)triazenido] 2 (C 5 H 5 N) 2 Estela dos Reis Crespan 2005

N 1,N 3 -bidentate ligand [Hg(N 3 (Ph(OCH 3 )) 2 )(Cl)] M. R. Melardi; Analytical Sciences 2007

N 1,N 3 -bidentate bridging ligand [Pd(PhN 3 C 4 H 8 N 3 Ph)] 2 Estela dos Reis Crespan 2005

N 1,N 3 -tridentate bridging ligand [Tl(RC 6 H 4 N 3 C 6 H 4 R)] 2 Inorganica Chimica Acta 2006

N 1,N 3 -tetradentate bridging ligand [Tl(NO 2 C 6 H 4 N 3 C 6 H 4 NO 2 )] 2 Estela dos Reis Crespan 2005

Preparation methods of Aryltriazene complexes with metals There are several methods to prepare this complexes; Such as: 1.Reaction of metal carboxylate with Aryltriazenes(1941). 2.Reaction of metal halide with Lithium triazenid complex (1973). 3.Reaction of metal salt with Aryltriazene next to triethylamine & heat(2003). 4.Reaction of metal hydride or metal alkyl with Aryltriazene (1979). etc …

Experimental...

1,3-bis(2-methoxyphenyl)triazene synthesis M.p= °C M.w= g.mol -1 Yield= % Anal. Sci Single crystals in diethylether were obtained.

Mercury complex preparation Hg (s) + Hg 2+ (aq) [Hg 2 ] 2+ (aq) M.p= °C M.w= g.mol -1 Yield= % L= 1,3-bis(2-methoxyphenyl)triazene Inorganica Chimica Acta 2007

Elemental Analysis Mercury identification in complex using diphenylcarbazide using Sodium hydroxide (especially for Hg 2+ ion) Hg OHˉ HgO + H 2 O using Potassium iodide Hg 2+ (aq) + 2I (aq) HgI 2

IR spectra Ligand Complex Spectroscopic studies

1 H-NMR spectra Ligand Complex

13 C-NMR spectra Ligand Complex

Molecular structure of Mercury complex

ORTEP view of Mercury complex

Crystal packing fragment along a crystal axes

C 28 H 28 HgN 6 O 4 Molecular formula Molecular weight Orthorhombic, Pna21System, space group a = (3) Å b= (6) Å c= (8) Å α= β= γ= 90° Unit cell dimensions (17) Å 3 Volume 4Z Mg/m 3 Density Needle-like, redCrystal view 0.23 × 0.18 × 0.10 mm 3 Crystal size Crystal data for Mercury complex

(I) (II) [Hg(N 3 (Ph(OCH 3 )) 2 )(Cl)][Hg(RC 6 H 4 N 3 C 6 H 4 R) 2 Py]

1,3- bis(2-cyanophenyl)triazene was synthesized first time like to 1,3- bis(2-cyanophenyl)triazene. M.p= °C M.w= g.mol -1 Yield= % Single crystals in diethylether were obtained.

Mercury complex preparation L=1,3- bis(2-cyanophenyl)triazene Decomposes at °C M.w= g.mol -1 Yield= %

Mercury identification in complex using diphenylcarbazide using Sodium hydroxide (especially for Hg 2+ ion) Hg OHˉ HgO + H 2 O Elemental analysis

UV-Visible spectra Spectroscopic studies

IR spectra Ligand Complex

1 H-NMR spectra Ligand Complex

13 C-NMR spectra Ligand Complex

X-ray diffraction crystallography For Mercury complex we found the answer below from operator: But the crystal structure of 1,3-bis(2-cyanophenyl)triazene ligand was determined.

Centrosymmetric H-bonded dimmers of molecules of type A & A'.

General view of molecule of type A & A'.

Stacking interaction between molecules of type A & A.

Crystal packing of 1,3-bis(2-cyanophenyl)triazene

conclusion Elemental analysis & spectroscopic studies show that two kind of complex containing Aryltriazene & Hg cation were formed. Molecular & crystal structure of [Hg(CH 3 OC 6 H 4 N 3 C 6 H 4 OCH 3 ) 2 ] were determined by X-ray diffraction method. The complex crystallizes in Orthorhombic crystal system & and Pna21 space group. Crystal structure of complex of Hg cation & 1,3-bis(2-cyanophenyl)triazene was not determined; but studies show that the ML 2 complex was formed.

Special thanks to: Dr. Mohammad R. Melardi Dr. Mohammad K. Rofouei Dr. Saeed Dehghanpour Dr. Mohammad R. Talei