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Chapter 23: Problem 96

A palladium complex formed from a solution containing bromide ion and pyridine, \(\mathrm{C}_{5} \mathrm{H}_{5} \mathrm{N}\) (a good electron-pair donor), is found on elemental analysis to contain 37.6\(\%\) bromine, 28.3\(\%\) carbon, 6.60\(\%\) nitrogen, and 2.37\(\%\) hydrogen by mass. The compound is slightly soluble in several organic solvents; its solutions in water or alcohol do not conduct electricity. It is found experimentally to have a zero dipole moment. Write the chemical formula, and indicate its probable structure.

Short Answer

Expert verified
The empirical formula of the palladium complex is PdBrC₅H₅N. Its probable square-planar structure consists of a central palladium atom coordinated with two bromine atoms above and below and two pyridine ligands on adjacent sides, creating a symmetrical and non-polar structure with a zero dipole moment: Br | N - Pd - N | Br

Step by step solution

01

Calculate moles of each element

To find the moles of each element, we will use the given mass percentage and divide by the respective molar mass. Let's assume a 100 g sample, so the mass% will be equal to the mass of the element in the sample. Moles of Br = (37.6 g) / (79.90 g/mol) = 0.4706 mol Moles of C = (28.3 g) / (12.01 g/mol) = 2.36 mol Moles of N = (6.60 g) / (14.01 g/mol) = 0.471 mol Moles of H = (2.37 g) / (1.01 g/mol) = 2.35 mol
02

Calculate mole ratios of each element

Now, let's find the mole ratio for each element by dividing the moles of each element by the smallest number found in the previous step. Mole ratio of Br = 0.4706 mol / 0.4706 mol = 1 Mole ratio of C = 2.36 mol / 0.4706 mol = 5 Mole ratio of N = 0.471 mol / 0.4706 mol = 1 Mole ratio of H = 2.35 mol / 0.4706 mol = 5
03

Determine Empirical Formula

Using the mole ratios from Step 2, we can now write the empirical formula for the palladium complex as: BrC₅H₅N However, we also need to include Palladium in the formula. Since we know the whole complex is neutral and pyridine could coordinate with the metal as a ligand similar to ammonia, we can write the empirical formula as: PdBrC₅H₅N
04

Propose Probable Structure

The information that the compound has a zero dipole moment suggests that the complex has a symmetrical structure. Based on this, we can propose the following probable square-planar structure for the palladium complex: Br | N - Pd - N | Br In this structure, the palladium atom is in the center with bromine atoms above and below and pyridine ligands replacing two adjacent hydrogen atoms in the aromatic ring on both sides. This arrangement results in a symmetrical and non-polar structure with a zero dipole moment.

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Most popular questions from this chapter

For each of the following compounds, determine the electron configuration of the transition-metal ion. \((\mathbf{a})\) TiO, \((\mathbf{b}) \mathrm{TiO}_{2},(\mathbf{c}) \mathrm{NiO},(\mathbf{d}) \mathrm{ZnO}\) .

Which periodic trend is partially responsible for the observation that the maximum oxidation state of the transition-metal elements peaks near groups 7 \(\mathrm{B}\) and 8 \(\mathrm{B} ?\) (a) The number of valence electrons reaches a maximum at group 8 \(\mathrm{B} .\) (b) The effective nuclear charge increases on moving left across each period. (c) The radii of the transition-metal elements reach a minimum for group \(8 \mathrm{B},\) and as the size of the atoms decreases it becomes easier to remove electrons.

Which transition metal atom is present in each of the following biologically important molecules: (a) hemoglobin, (b) chlorophyls, (c) siderophores, (d) hemocyanine.

(a) In early studies it was observed that when the complex \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{4} \mathrm{Br}_{2}\right] \mathrm{Br}\) was placed in water, the electrical conductivity of a 0.05\(M\) solution changed from an initial value of 191 \(\mathrm{ohm}^{-1}\) to a final value of 374 \(\mathrm{ohm}^{-1}\) over a period of an hour or so. Suggest an explanation for the observed results.(See Exercise 23.69 for relevant comparison data.) (b) Write a balanced chemical equation to describe the reaction. (c) \(A 500\)-mL solution is made up by dissolving 3.87g of the complex. As soon as the solution is formed, and before any change in conductivity has occurred, a 25.00-mL portion of the solution is titrated with 0.0100 \(\mathrm{M} \mathrm{AgNO}_{3}\) solution. What volume of AgNO \(_{3}\) solution do you expect to be required to precipitate the free \(\operatorname{Br}^{-}(a q) ?(\mathbf{d})\) Based on the response you gave to part (b), what volume of \(\mathrm{AgNO}_{3}\) solution would be required to titrate a fresh 25.00 -mL sample of \(\left[\mathrm{Co}\left(\mathrm{NH}_{3}\right)_{4} \mathrm{Br}_{2}\right] \mathrm{Br}\) after all conductivity changes have occurred?

Give the number of (valence) \(d\) electrons associated with the central metal ion in each of the following complexes: (a) \(\mathrm{K}_{3}\left[\mathrm{TiCl}_{6}\right],(\mathbf{b}) \mathrm{Na}_{3}\left[\mathrm{Co}\left(\mathrm{NO}_{2}\right)_{6}\right],(\mathbf{c})\left[\mathrm{Ru}(\mathrm{en})_{3}\right] \mathrm{Br}_{3},\) \((\mathbf{d})[\mathrm{Mo}(\mathrm{EDTA})] \mathrm{ClO}_{4},(\mathbf{e}) \mathrm{K}_{3}\left[\mathrm{ReCl}_{6}\right].\)
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