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Chapter 7: Problem 3

Name the octahedral complex ions (a) cis- \(\left[\mathrm{CrCl}_{2}\left(\mathrm{NH}_{3}\right)_{4}\right]^{+}\), (b) trans- \(\left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{sN}-\mathrm{NCS})_{4}\right]^{-}\), (c) \(\left[\mathrm{Co}\left(\mathrm{C}_{2} \mathrm{O}_{4}\right)(\mathrm{en})_{2}\right]^{+}\).

Short Answer

Expert verified
(a) Cis-tetramminedichloridochromium(III) ion, (b) Trans-diammine-tetrathiocyanato-S-chromium(III) ion, (c) Bis(ethylenediamine)(oxalato)cobalt(III) ion.

Step by step solution

01

Identify the Ligands

For each complex, identify the ligands present and classify them based on their charge and name. Note that "cis" and "trans" describe the arrangement of ligands around the central atom.(a) For \( \left[\mathrm{CrCl}_{2}\left(\mathrm{NH}_{3}\right)_{4}\right]^{+} \), the ligands are \( \mathrm{Cl}^- \) (chlorido) and \( \mathrm{NH}_{3} \) (ammine).(b) For \( \left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{sN}-\mathrm{NCS})_{4}\right]^{-} \), the ligands are \( \mathrm{NH}_{3} \) (ammine) and \( \mathrm{NCS}^- \) which can be named as thiocyanato (note the 'sN-' indicates in this context the sulfur bonding to the central metal).(c) For \( \left[\mathrm{Co}\left(\mathrm{C}_{2}\mathrm{O}_{4}\right)(\mathrm{en})_{2}\right]^{+} \), the ligands are \( \mathrm{C}_{2}\mathrm{O}_{4}^{2-} \) (oxalato) and \( \mathrm{en} \) (ethylenediamine).
02

Determine the Oxidation State of the Central Metal

Calculate the oxidation state of the central metal in each complex by considering the charges of the ligands and the overall charge of the complex.(a) For \( \left[\mathrm{CrCl}_{2}\left(\mathrm{NH}_{3}\right)_{4}\right]^{+} \), let the oxidation state of Cr be \( x \). The equation is: \( x + 2(-1) + 4(0) = +1 \). So, \( x = +3 \).(b) For \( \left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{sN}-\mathrm{NCS})_{4}\right]^{-} \), let the oxidation state of Cr be \( x \). The equation is: \( x + 2(0) + 4(-1) = -1 \). So, \( x = +3 \).(c) For \( \left[\mathrm{Co}\left(\mathrm{C}_{2}\mathrm{O}_{4}\right)(\mathrm{en})_{2}\right]^{+} \), let the oxidation state of Co be \( x \). The equation is: \( x + (-2) + 2(0) = +1 \). So, \( x = +3 \).
03

Name the Complex Ions

Combine the ligand names with the oxidation state of the metal to form the full name of each complex, indicating the geometrical configuration when necessary.(a) The name for \( \left[\mathrm{CrCl}_{2}\left(\mathrm{NH}_{3}\right)_{4}\right]^{+} \) is **cis-tetramminedichloridochromium(III) ion**.(b) The name for \( \left[\mathrm{Cr}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{sN}-\mathrm{NCS})_{4}\right]^{-} \) is **trans-diammine-tetrathiocyanato-S-chromium(III) ion**.(c) The name for \( \left[\mathrm{Co}\left(\mathrm{C}_{2}\mathrm{O}_{4}\right)(\mathrm{en})_{2}\right]^{+} \) is **[bis(ethylenediamine)(oxalato)cobalt(III) ion]**.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Ligand Classification
In coordination chemistry, classifying ligands is crucial. Ligands are ions or molecules that bind to a central metal atom to form coordination complexes. They can be classified based on their charge and the number of donor atoms used in bonding. Ligands can be:
  • Neutral: Such as water ( H鈧� 鈧侽), and ammonia ( NH鈧� 鈧�).
  • Anionic: Examples include the chlorido ligand ( Cl鈦� ), oxalato ( C鈧侽鈧� 鈧勨伝虏 o), and thiocyanato ( NCS鈦� ).
  • Cationic: Rare but possible, like NO鈦� i (nitrosyl).
  • Polydentate: Ligands like ethylenediamine ( 'en' ) and oxalate ( C鈧侽鈧� 鈧劼测伝 s). They attach through more than one atom, forming chelates.
In the given complexes, for instance, ammonium is a neutral monodentate, while oxalate and ethylenediamine are polydentate. Understanding ligand classification helps in determining properties and naming coordination compounds.
Oxidation State Determination
Oxidation states play a key role in identifying the chemistry of coordination complexes. Determining the oxidation state involves looking at the charges of the ligands and the overall charge on the complex. Here's how it's done:
  • Write the formula of the complex.
  • Set up an equation where the sum of the oxidation state of the central metal and the charge of all ligands matches the overall charge of the complex.
Let's consider the complex [CrCl鈧�(NH鈧掆們鈧�)]鈦� with oxidation state, referred to as 'x'. The ligands Cl鈦� contribute -1e each, and NH鈧掆們 is neutral. Hence,\[ x + 2(-1) + 4(0) = +1 \]Solving gives 'x' = +3.Repeat the process for other complexes to reach their oxidation states. Mastering this determination will aid in naming the compounds because the oxidation state becomes part of the compound's name.
Geometrical Isomerism
Geometrical isomerism is a fascinating aspect of coordination chemistry that arises in some complex compounds. It occurs when ligands can take different positions around the central metal atom, resulting in different spatial arrangements. This isomerism is prevalent in octahedral complexes. Examples include:
  • Cis- where similar ligands are adjacent.
  • Trans- where similar ligands are opposite each other.
For the complexes discussed, cis- [ CrCl鈧�(NH鈧� 鈧冣倓)]+ and trans- [ Cr(NH鈧� 鈧冣們(NCS)鈧�)]鈦� illustrate this concept. The cis arrangement occurs when chlorides in the complex are next to each other, while trans suggests that thiocyanates are positioned opposite. This type of isomerism drastically affects the chemical properties and biological activities of compounds, thus, understanding it is vital in the study of coordination chemistry.
Coordination Chemistry
Coordination chemistry forms the backbone of understanding how complex ions interact and stabilize. It involves studying compounds where central metal atoms are surrounded by molecules or ions, termed ligands. The coordination sphere includes both the central metal and its attached ligands. In naming these complexes:
  • The ligands are listed in alphabetical order.
  • The oxidation state of the metal, determined as before, follows the metal's name in Roman numerals within parentheses.
  • Prefixes like tetra-, penta-, or hexa- indicate the number of identical ligands.
For instance, the name "cis-tetramminedichloridochromium(III)" indicates four ammine ligands, two chlorido ligands, and a chromium metal with an oxidation state of +3. Coordination chemistry not only aids in nomenclature but plays a huge role in fields like bioinorganic chemistry, catalysis, and materials science.

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Most popular questions from this chapter

Which of the following complexes are chiral? (a) \(\left[\mathrm{Cr}(\mathrm{ox})_{3}\right]^{3-}\), (b) cis- \(\left[\mathrm{Pt} \mathrm{Cl}_{2}(\mathrm{en})\right],(\mathrm{c}) \mathrm{cis}-\left[\mathrm{RhCl}_{2}\left(\mathrm{NH}_{3}\right)_{4}\right]^{+}\), (d) \(\left[\mathrm{Ru}(\mathrm{bpy})_{3}\right]^{2+},(\mathrm{c})\) \(\mathrm{fac}-\left[\mathrm{Co}\left(\mathrm{NO}_{2}\right)_{3}(\right.\) dien \(\left.)\right]\), (f) mer- \(\left[\mathrm{Co}\left(\mathrm{NO}_{2}\right)_{3}(\right.\) dien \(\left.)\right] .\) Draw the enantiomers of the complexes identified as chiral and identify the plane of symmetry in the structures of the achiral complexes.

Draw both \(\Lambda\) and \(\Delta\) isomers of the \(\left[\mathrm{Ru}(\mathrm{en})_{3}\right]^{2+}\) cation.

Name and draw structures of the following complexes: (a) \(\left[\mathrm{Ni}(\mathrm{CN})_{4}\right]^{2-}\), (b) \(\left[\mathrm{CoCl}_{4}\right]^{2-}\), (c) \(\left[\mathrm{Mn}\left(\mathrm{NH}_{3}\right)_{6}\right]^{2+}\)

For which of the following square-planar complexes are isomers possible? Draw all the isomers. \(\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2}(\mathrm{ox})\right],\left[\mathrm{PdBrCl}\left(\mathrm{PEt}_{3}\right)_{2}\right]\) \(\left[\operatorname{lrH}(\mathrm{CO})\left(\mathrm{PR}_{3}\right)_{2}\right],\left[\mathrm{Pd}(\mathrm{gly})_{2}\right]\)

The two compounds \(\left[\mathrm{RuBr}\left(\mathrm{NH}_{3}\right)_{5}\right] \mathrm{Cl}\) and \(\left[\mathrm{RuCl}\left(\mathrm{NH}_{3}\right)_{5}\right] \mathrm{Br}\) are what types of isomers?
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