You are on page 1of 6

Experiment 1: Determination of Some Structural Features of Metal Complexes by

Infra-Red Spectroscopy
Ong Zhy Hui
21572185 7th Feb 2017

Title: Experiment 1 Determination of Some Structural Features of Metal Complexes
by Infra-Red
Spectroscopy

Aims:
Part A: To prepare cis- and trans- isomers of big glycinato Cu(II) and to identify
the stereochemistry of
the complexes by using infra-red spectroscopy and the principles of group
theory.
Part B: To prepare a Cu(II) complex of dimethyl sulfoxide (DMSO) and to
determine the coordination
mode (O- or S-bound) for DMSO complexes of three different metal ions:
Cu(II), Ru(II) and Pd(II).
To compare experimental results with assignments predicted by the principle
of Hard and Soft
Acids and Bases.

Abstract:
Part A: The Isomers for Cu(gly-)2.H2O are both synthesized. The weight and the
percentage of yield of the
products are recorded and calculated. The IR Spectra for Isomer 1 and Isomer
2 (with 2 methods)
are also studied. The functional groups are identified with the IR Spectra and
the Frequency
Range for different bond type.

Part B: CuCl2.2DMSO was synthesised and studied. Dimethylsulfoxide (DMSO) is
an ambidentate ligand,
which it has two different sites in which an atom can bind to. These two sites
are either sulphur
or oxygen on DMSO. Using infrared spectroscopy, the site in which Pd, Ru and
Cu bind to on
DMSO can be determined by the absorption of the S=O bond, which absorbs
at around 1050cm-1. So the IR spectrum of the, PdCl2.2DMSO, RuCl2.4DMSO
and CuCl2.2DMSO were measured.

Methods:
Part A: Preparation and Characterisation of the Geometric Isomers of a
Coordination Complex: Cis- and
Trans- Bis Glycinato Copper (II) Monohydrates

Preparation of Cu(gly-)2.H2O Isomer 1 - Copper (II) acetate monohydrate (2.0 g)
is dissolved in
hot deionized water (25 ml) in a 100 ml Erlenmeyer flask. Hot ethanol (25 ml)
is added to the
solution and the temperature is maintained at about 70⁰C. Glycine (1.5 g) is
dissolved in hot
deionized water (25 ml) in a separate Erlenmeyer flask. The two solutions are
Page | 1

(0. A light green product is yielded by the immediate exothermic reaction. The filtrate is preserved in a separate flask before washing the product with ethanol.H2O = 0.H2O (isomer 1).H2O Isomer 2 – (Method 1) Cu(gly-)2. extra glycine (1. [Cu(gly-)2. The product is collected by suction filtration using a Buchner funnel. (Method 2) - Cu(gly )2.0 g) and the filtrate preserved from the above reaction (10 ml) are placed into a 100 ml round bottom flask.65 g mol-1 Weight of Cu(II)(OAc)2. The solid is removed from the oven and cooled to room temperature.H2O = 199. The product is washed with two 2 ml portions of cold ethanol.5 g).000 g Moles of Cu(II)(OAc)2. The product is dried in a vacuum desiccator. The precipitation of the product is completed by transferring the flask into an ice-water bath for about 10 minutes.H2O (isomer 1).2DMSO – Copper (II) chloride (670 mg. Preparation of Cu(gly-)2. The mixture is carefully heated on an oil bath at reflux for 1 hour. The mixture is stirred for a few minutes.01000 mols Page | 2 . The reaction shown below is completed in 30 minutes.H2O = 2.2 g) is placed in an evaporating dish and heated in an oven at about 180⁰C. DMSO (1 ml) is slowly added to the stirred solution.H2O (isomer 1)] (s) → [Cu(gly-)2 (isomer 2)] (s) + H2O (g) Part B: Metal Complexes of Dimethyl Sulfoxide (DMSO) Preparation of CuCl2. The solid is collected by suction filtration using a Buchner funnel and air dried. (1. The product is collected by a vacuum filtration using a Hirsch funnel.H2O Isomer 1 Formula weight of Cu(II)(OAc)2. Results: Part A: Preparation of Cu(gly-)2. followed by equal portions of diethyl ether.Experiment 1: Determination of Some Structural Features of Metal Complexes by Infra-Red Spectroscopy Ong Zhy Hui 21572185 7th Feb 2017 mixed while hot and gently swirl the flask. 5 mmol) is dissolved in ethanol (5 ml) in a 10 ml Erlenmeyer flask equipped with a stirrer bar. The resulting mixture is cooled to room temperature.

00920 mols Equation for reaction: (CH3CO2)2Cu.H2O Isomer 1 = ×100 0.00% Preparation of Cu(gly-)2.47% Part B: Preparation of CuCl2.H2O + 2NH2CH2CO2H  Cu(NH2CH2COO)2.231 g Moles of product (Isomer 2 – Method b) = 0.68 g mol- 1 Weight of Isomer 1 used = 1.00534 × 100 0.00920 % yield of Cu(gly-)2.500 g Moles of Isomer 1 used = 0.00101 ×100 0.H2O Isomer 2 Formula weight of product Cu(gly-)2.H2O Isomer 2 – Method a = 0.H2O Isomer 2 – Method b = 0.68 -1 g mol Weight of product (Isomer 2 – Method a) = 1.2DMSO Page | 3 .H2O + 2CH3COOH 0.00101 mols % yield of Cu(gly-)2.113 g Moles of product = 0.H2O (Isomer 1) = 229.01000 = 92.68 -1 g mol Weight of product (Isomer 2 – Method b) = 0.226 g Moles of product (Isomer 2 – Method a) = 0.Experiment 1: Determination of Some Structural Features of Metal Complexes by Infra-Red Spectroscopy Ong Zhy Hui 21572185 7th Feb 2017 Formula weight of product Cu(gly-)2.00534 mols % yield of Cu(gly-)2.78% Formula weight of product Cu(gly-)2.H2O (Isomer 2 – Method a) = 229.00653 = 81.00653 = 15.H2O = 229.00653 mols Formula weight of product Cu(gly-)2.68 g mol-1 Weight of product = 2.H2O (Isomer 2 – Method b) = 229.

00504 = 84. 1117.72 g mol-1 Weight of product = 1. Ethers.08 – 3261.9 cm-1 Sulphur 1096.00504 mols Formula weight of product CuCl2.74 C-C Aromatic C-C bond 1383.87 – 3157.2DMSO = × 100 0.2DMSO= 290.50 C-O Esters.48 g mol-1 Weight of copper (II) chloride = 0. Ethers.Experiment 1: Determination of Some Structural Features of Metal Complexes by Infra-Red Spectroscopy Ong Zhy Hui 21572185 7th Feb 2017 Formula weight of copper (II) chloride = 170.4DMSO cm-1 CuCl2.9 cm-1 Oxygen Discussion: Part A: (i) Table 2: Functional group frequencies for the glycine ligands of the two complexes. Type of Frequency (cm-1) Bond Type Functional Group Complexes Hydrogen Bonded 3330. RuCl2.242 g Moles of product = 0.09 O-H Alcohols 1573.53 C-C Aromatic C-C bond 1385.72% Table 1: IR peaks of PdCl2.14 C-H Alkanes Isomer 1 1319.4DMSO & CuCl2.00427 mols Equation for reaction: CuCl2 + 2DMSO  CuCl2.2DMSO 915.2DMSO.2DMSO 1089. 1149.4 Sulphur & Oxygen RuCl2.12 C-H Alkanes Isomer 2 1328.2DMSO 0.49 C-N Amines Alcohols.00427 % yield of CuCl2.2DMSO from IR Spectra DMSO Coordinated by Sulphur IR Peaks Complexes or Oxygen PdCl2.58 O-H Alcohols 1605.88 C-O Esters. Carboxylic Acids Page | 4 . Carboxylic Acids Hydrogen Bonded 3309.01 – 1583.76 C-N Amines Alcohols.860 g Moles of copper (II) chloride = 0.3 cm-1 & 922.

This showed that the stereochemistry of Isomer 1 is in cis. As DMSO can act as a hard and soft base. it can be soft acid and hard acid.H2O Isomer 2 – Method a is 81. The experiment results conform to the principle of Hard and Soft Acids and Bases (HSAB). then the metal should be a hard acid as the metal will form a bond with a lone pair from the oxygen. it will form stable complexes when it binds to PPh 3 (soft base). it will form stable complexes when it binds to CO & PPh 3 (soft bases). it will form stable complexes when it binds to CO & PPh 3 (soft bases). PdCl 2 binds to Sulphur which indicated that it is a soft acid.& H2O (hard bases). The result of bonding with a long pair will decrease the absorption frequency. This is because metal is donating electrons to the Sulphur atoms which increases the absorption frequency. 3. For a metal that bind to Sulphur atoms.form and Isomer 2 is in trans. Cr3+ is a hard acid. Therefore. Fe0 is a soft acid. 2. then metals could be able to bind to a DMSO as soft and hard acid. then the metal is a soft acid. Rh+ is a soft acid.47%.atom. Yes.form. I predict that the DMSO is coordinated to Ni(II) by the O. it is only 15. Part B: 1. Whereas Isomer 2 shows only 1 each for the number of Cu-O and Cu-N Infra-red stretches.00%. it will form stable complexes when it binds to C 2O42.H2O Isomer 1 is 92.78% whereas for Method 2. CuCl2 binds to the oxygen indicates that it is a hard acid. Conclusions: Part A: The percentage yield obtained for the product Cu(gly -)2. RuCl 2 binds to both Sulphur and Oxygen sites. which indicates that it is a hard acid.Experiment 1: Determination of Some Structural Features of Metal Complexes by Infra-Red Spectroscopy Ong Zhy Hui 21572185 7th Feb 2017 (ii) Isomer 1 shows 2 number of Cu-O Infra-red stretches and 2 number of Cu- N Infra-red Stretches. this result is consistent with that expected based on the principle of Hard and Soft Acids and Bases (HSAB). The percentage yield obtained for the product Cu(gly-)2. The functional groups for both Isomer 1 and 2 are Page | 5 . Au+ is a soft acid. For a metal that binds to oxygen atom. Based on the IR result.

Ethers.72%. JR. Bora and M. India (September 24 th. Metals have been identified as either soft or hard acid by using the Hard and Soft Acids and Bases (HSAB) theory and the IR spectra. C-N bond (Amines) and C-O bond (Alcohols. GOEL Department of Chemistry. 1971 Page | 6 . M. Esters. E. C-H bond (Alkanes). C-C bond (Aromatic C-C bond). AND R. Dibrugarh University. Guelph. Both isomer 1 & 2 showed that the significant functional group are O- H bond (Hydrogen bonded Alcohols). Ontario. ‘Canadian Journal of Chemistry’.. For Pd is a soft acid. Singh* Department of Chemistry.Experiment 1: Determination of Some Structural Features of Metal Complexes by Infra-Red Spectroscopy Ong Zhy Hui 21572185 7th Feb 2017 identified and tabulated in Table 2. May 6. G. MASLOWSKY. References: 1.atom of DMSO whereas Cu is a hard acid. SENOFF.& S. 1977) 2. C. Ru is both a hard & soft acid as it can bind to both O. Carboxylic Acids). T.2DMSO is 84. Part B: The percent yield obtained for the product CuCl 2. V. University of Guelph. ‘Sulphoxide Complexes of Ruthenium’ Assam.