Studies of Complexes of Para Bromo Phenyl mercury Thiocyanates with M| (BIS Salicylidene 1:2 propane diamine)

The Lewis base character of organomercury thiocyanates has been explored and few organometallic compounds we have study. Here we report the preparation and study of organometallic compound of general formula (RHgSCN)2 M(NCS)2 [R=P-Bromophenyl: M= Co (II). Ni(II), Cu(II), Zn(II), Mn (II)]. The complexes have been synthesized by reacting RHgSCN with M(NCS)2. These compounds also act as Lewis acids on account of unsaturation at M and at Hg. Due to this unsaturation they have been reacted with M (Salpn) ]M = Co(II), Ni(II), Cu(II), Zn(II), Salpn -=(C17H16N2O2)]. Structure of these complexes has been established on the basis of different physico-chemical methods. K E Y W O R D S Mercury | Bromo Phenyl |Salicylidene | Organomercury | Thiocyanates C I T A T I O N Amit Kumar Giri, Deep Saurabh Singh, Suresh Kumar :Effect of monocrotophos on small intestine of mice. ESSENCE Int. J. Env. Rehab. Conserv. IX (1): 142—151. https://doi.org/10.31786/09756272.18.9.1.117 https://eoi.citefactor.org/10.11208/essence.18.9.1.117 Original Research Article Studies of Complexes of Para Bromo Phenyl mercury Thiocyanates with M (BIS Salicylidene 1:2 propane diamine) Giri, Amit Kumar; Singh, Deep Saurabh and Kumar, Suresh Department of Industrial Chemistry, R.S.M. College, Dhampur, Uttarakhand Deparment of Chemistry, Govt. PG College, Rishikesh, Uttarakhand Corresponding Author: dramitkumargiri@gmail.com International Journal for Environmental Rehabilitation and Conservation ISSN: 0975 — 6272 IX (1): 142— 151 www.essence-journal.com A R T I C L E I N F O Received: 23 January 2018 | Accepted: 22 April 2018 | Published Online: 15 August 2018 DOI: 10.31786/09756272.18.9.1.117 EOI: 10.11208/essence.18.9.1.117 Article is an Open Access Publication. This work is licensed under Attribution-Non Commercial 4.0 International (https://creativecommons.org/licenses/by/4.0/) ©The Authors (2018). Publishing Rights @ MANU—ICMANU & ESSENCE—IJERC. ESSENCE—IJERC | Amit et al. (2018) | IX (1): 142—151 143 Introduction There has been considerable interest in the co. ordination chemistry of transition metal involving nitrogen & oxygen donors ligands due to increasing recognition of the role of this metal in biological system. These complexes are significant not only for their redox-active role in several biochemical processes but also for the diversity in their magnetic behavior. Manganese complexes containing tetra co-ordinating ONNO donor ligands are well studies as the structural models of active site of many in Metallo enzymes. The most important operation showed by Mn in Nature is the Photolytic Oxidation of water of Dioxygen in the oxygen evolving complex (OEC) of photo system – II (PS II) found in the photo synthetic apparatus of green plants and certain cyanobacteria. The chemistry of carbohydrazide compound has been studies by Swany & Siddalingaiah. Variety of metal complexes of symmetrical dihydrazones derived from thiocarbohydrazides have been synthesized and their stereo chemistry is also reported. Hydrozones and their complexes with transition metals have provoked wide interest for their apparent biological and pharmaceutical activities. Some carbohydrazon ligands behave as N, Nchelating agent in the Neutral form and an ONNO(NNO-Chelating agent in deprotonated from, Warad et.al have synthesized and characterized the carbohydrazone bis (salicylaldhyde) ligand and its transition metal complexes. They proposed that this ligand act as a dinegative tetradentate (N2O2) ligand in forming a tetrahedral complexes. Complexes of carbohydrazide with non transition metal ion such as organotin (IV) have not received much attention. Affan et. al have reported a new series of di organotin (IV) complexes by the reaction of R2 Sn Cl2 (R= Me, Bu, Ph) with O, N, O – tridentate carbohydrazone ligand derived from carbohydrazide. The structure have been established on the basis of IR & X -ray Studies. Experimental Reagent grade solvents were purified and dried before use para bromo aniline was used from fresh bottles. Para bromo phenyl mercury chloride was prepared by diazotinzation method (1-3) as discussed below: Preparation of Para Bromo Phenyl Chloride (P-BrC6H4HgCl):17.2 gms (0.1 mole) of Pbromo aniline was added to a mixture of 50 ml of concentrated hydrochloric acid and 50 ml of water. The mixture was cooled by adding ice and stirred vigorously. The temperature of the reaction was maintained between 0 to 5C and solid sodium nitrite (7.0 g, 0.1 mole) was added in small fractions. After stirring for about half an hour, the whole mass was filtered. To the clear filrate a cooled solution of (27.0 g, 0.1 mole) mercuric chloride in 30 ml of concentrated hydrochloric acid was slowly added with vigorous stirring. The stirring was continued for 15 minutes more and the precipitate was filtered, washed with water, followed by ether and dried in air. The pBrC6H4N2HgCl so obtained was mixed with 12 gram of copper powder in 100 ml of cold water in fraction with stirring. The mixture was stirred for one hour and allowed to stand overnigh and filtered. The residue was extracted with eylene, which on cooling gave white crystals of P -BrC6H4HgCl. Preparation of Para Bromo Phenyl Mercury Thiocyanate P-BrC6H4HgSCN: Para bromo phenyl Mercury chloride was converted into its thiocyanate derivative by reacting with potassium thiocyanate in 1:1 molar ratio in acetone. The potassium bromide was filtered off and the filrate was concentrated by vacuum evaporation on addition of water to the concentrate solution, p-bromo phenyl mercury thiocyanate separated, which was followed by ether and dried in air. The compound was recrystallized from acetone. The purity of the thiocyanate derivative was tested by elemental analysis and infra-red spectral measurement.p-BrC6H4HgSCN. m.p. 195°C Found Nitrogen 3.30%, Sulphur 7.60%, Mercury 48.20%Calculated Nitrogen 3.37%, Sulphur 7.71%, Mercury 48.38% Infra red spectral band position. V (C-N) 2180 cm, v (C-S) 765 cm, d(NCS) 440 cm. ESSENCE—IJERC | Amit et al. (2018) | IX (1): 142—151 144 Preparation of Lewis Acid [(p-BrC6H4HgCN)2 M(NCS)2: [M=Co(II), Ni(II), Cu(II), Zn(II), Mn (II)] 1 mole of metal thiocynate prepared from their respective metal nitrates by the reaction of potassium thiocynate, was suspended in acetone and was reacted with 2 m mole of pBrC6H4HgSCN in the same solvent. The mixture was stirred first for two hours and then refluxed for twelve hours. The compound thus formed was filtered, washed with the ether, acetone and dried in vacuum. The Lewis acid of cobalt and nickel were also prepared by heating their corresponding pyridine complexes (p-BrC6H4HgSCN)2Co(NCS)2 (Py)2 and (p-BrC6H4HgCN)-2 Ni(NCS)2 Py2 to get a good yield of the Lewis acids. Preparations of M (Salpn): [M = Co(II), Ni(II), Cu(II), Zn(II), Salpn= (C17H16N2O2)]:5.76 gm of salicylaldehyde was dissolved in 65 ml of 95% ethanol. 2.03 gm of 1:2-propane diamine was also dissolved in the same volume of ethanol. This solution was slowly added to the solution of salicylaldehyde with continuous stirring on an ice bath. The schiffs base precipitated which was dissolved by heating to 60°C, 5.76 gm of cobalt acetate tetrahydrate was dissolved in 30 ml of water and heated to 60°C the Cobaltous acetate solution was rapidly poured into the alcoholic solution of the schiff's base and well shaken. A brown gelatinous product was formed which rapidly changed into large red cyrstals. M((Salpn): [M = Co(II), Ni(II), Cu(II), Zn(II), were similarly prepared by using their respective hydrated metal acetates in place of cobalt analogue. These schiff's base complexes were referred to as M(Salpn) and used as ligands. Preparation of Trimetalic Complexes [(RHgSCN)2 M(NCS)2 M (Salpn)] M = Co(II), Ni (II), Cu(II), Zn(II), Mn(II): =M = Co(II), Ni(II), Cu(II), Zn(II); R = p-BrC6H4 salpn = (C17H16N2O2)0.1 mole of (RHgSCN)2M(NCS)2 [R=p-bromo phenyl] and 1 mole of M (salpn) were separately dissolved in 100 ml of methanol or acetone, both the solutions were mixed and stirred for about 72 hours. The solid compound separated, which was filtered, washed with acetone and recrystallized from DMSO and dried in vacuum. Analysis of the complexes The complexes were analyzed for cobalt as anthranilate, nickel as dimethyl glyoximate, mercury as sulphide and zinc as zinc ammonium phosphate, sulphur was estimated as barium sulphate and nitrogen by semi-micro kjeldahls method. Analytical results along with M.Ps are presented in table 1-2. Physical Measurements The molar conductance of the complex were measured in dimethylsulphoxide (DMSO) using a Philips conductivity bridge model PR-9500. The magnetic susceptiblity measurements were made at room temperature by Gouy's method using HgCo(SCN)4 as standard. The infra red spectral measurements were made on Pye Unicam SP-3-300 spectrophotometer in the range 4000 cm -200 cm and the eletronic spectrophotometer. Results and Discussion Since Lewis acids "(RHgSCN)2 M(NCS)2" have unsaturation at M they been reacted with M (salpn) and the adducts of general formula (RHgSCN)2 M(NCS)2 M | (Co(II), Ni(II), Cu(II), Zn(II), Mn(II): =M = Co(II), Ni(II), Cu(II), Zn(II); salpn = (C17H16N2O2); R=p-Bromo phenyl] was obtained. The structure of these complexes has been established with the help of various physicochemical studies. The discussion is presented under the following heads: Lewis Acids On reaction with M(NCS)2 the RHgSCN form the complex of general formula formula (RHgSCN)2 M(NCS)2 [M =(Co(II), Ni(II), Cu(II), Zn(II), Mn (II); R=p-Bromo phenyl] which have been referred to as Lewis acids. Various studies ( reveal that cobalt, zinc and manganese have tetrahedral geometry in the Lewis acids (fig. 1). In case of nickel and copper Lewis acids the geometry is octahedral due to axial coordination of thiocyanate groups of other molecules of adjacent layers fig. 1