Coordination Chemistry

Question 1

This type of associativemechanism where no intermediate is formed and the rate does depends on the nature of the entering group.

Answer 1

Associative interchange mechanism

Bonding-making is more important than bond-breaking.

Question 2

The dissociative mechanism where no intermediate is formed and the rate does not depends on the nature of the entering group.

Answer 2

Dissociative interchange mechanism

Bonding-breaking is more important than bond-making.

Question 3

Idenfity the mechanism below.

Answer 3

Dissociative mechanism

The rate depends on breaking the bond of the leaving group.

Question 4

Idenfity the mechanism below.

Answer 4

Associative mechanism

The rate depends on the properties of the entering group and the encounter complex (intermediate)

Question 5

As the size of the leaving group increases, the rate of a associative mechanism ________.

Increases, Decreases, or No effect

Answer 5

No effect

Question 6

As the size of the entering group increases, the rate of an associative mechanism ________.

Increases, Decreases, or No effect

Answer 6

• *Decreases
• (Associative mechanisms are sensitive to the entering group and larger ligands tend to form unfavorable steric interactions with bound ligands)***

Question 7

As the size of the entering group increases, the rate of a dissociative mechanism ________.

Increases, Decreases, or No effect

Answer 7

No effect

(The rate determining step in a dissociative mechanism is breaking the metal-ligand bond)

Question 8

As the size of the metal increases, the rate of an associative mechanism ________.

Increases, Decreases, or No effect

Answer 8

Increases

(Large Coordination sphere favors associative mechanism )

Question 9

As the size of the metal increases, the rate of a dissociative mechanism ________.

Increases, Decreases, or No effect

Answer 9

Increases

Question 10

As the charge increases on the entering group, the rate of an associative mechanism ________.

Increases, Decreases, or No effect ​

Answer 10

Increases

Question 11

As the charge increases on the entering group, the rate of a dissociative mechanism ________.

Increases, Decreases, or No effect ​

Answer 11

No effect

(The rate determining step in a dissociative mechanism is breaking the metal-ligand bond)

Question 12

As the negative charge increases on the leaving group, the rate of an associative mechanism ________.

Increases, Decreases, or No effect ​

Answer 12

Decreases

Question 13

As the neagtive charge increases on the leaving group, the rate of a dissociative mechanism ________.

Increases, Decreases, or No effect ​

Answer 13

Decreases

Question 14

As the charge increases on the metal center, the rate of an associative mechanism ________.

Increases, Decreases, or No effect ​

Answer 14

Increases

Question 15

As the charge increases on the metal center, the rate of a dissociative mechanism ________.

Increases, Decreases, or No effect ​

Answer 15

Decreases

Question 16

As the M-L bond strength __________it becomes more difficult to remove the L, and the rate decreases for a dissociative mechanism.

Increases or Decreases

Answer 16

Increases

Question 17

Jahn-Teller ions have __________ water exchange rates.

Fast or Slow

Answer 17

Fast

Question 18

In what order should dimethyl sulfide and pyridine be adding to AuI₄^- below?

Answer 18

Dimethyl sulfide is more trans directing than iodine and pyridine

Question 19

What would be the Rh product of the reaction between [Rh(Cl)₃(CO)]^- and 1 eqv. PPh₃?

Answer 19

trans-[Rh(Cl)₂(CO)(PPh₃)]^-

Substitution occurs trans to the

strongest trans effect ligand CO > Cl^-

Question 20

Refers to the impact of a ligand on the strength of the bond trans to it in the ground state of a complex.

Answer 20

Trans influence (Structrual trans effect)

Ground State Property

Question 21

Refers to the impact of a ligand on the length of the bond trans to it in the ground state of a complex.

Answer 21

Trans influence (Structrual trans effect)

Ground State Property

Question 22

Chelate ligands form much more stable metal complexes than monodentate ligands.

Answer 22

Chelate Effect

Question 23

Refers to the observation that certain ligands increase the rate of ligand substitution when positioned trans to the departing ligand

Answer 23

Trans Effect [kinetic trans effect]

Both σ-donors and/or π-donors

Question 24

As the M-X bond strength increases, the rate of dissociative mechanism _____.

Increases or Decreases

Answer 24

Decreases

The rate determining step involves bond breaking

Question 25

**_Hard-Soft Theory:_** ## Footnote ***Soft Acids and Bases***

Answer 25

* **Highly polarizable** * **Typically large and low charge**

Question 26

## Footnote **The energy difference between the ground state CFSE and the transition state CFSE.**

Answer 26

**Crystal Field Activation Energy (CFAE)**

Question 27

**The stability that results from placing a transition metal ion in the crystal field generated by a set of point charges.**

Answer 27

**Crystal Field Stabilization Energy** **(CFSE)**

Question 28

**What nomenclature is** **the best description for the adduct below.**

Answer 28

**Side-on η² peroxo** η²- two oxygen atoms chelates side-on

Question 29

**What nomenclature is the best description of the adduct below.**

Answer 29

**Side-on η² superoxo** η²- two oxygen atoms

Question 30

**What nomenclature is the best description of the adduct below.​**

Answer 30

**Bis-(μ-oxo)** Bis-two oxygen atoms *μ-bridging*

Question 31

**Identify the best description of the O₂ adduct below.**

Answer 31

**μ-η² : η² peroxo** * μ-bridging* * η²-both oxygen coordinated*

Question 32

**Identify the best description of the O₂ adduct below.**

Answer 32

**Peroxo**

Question 33

**As the oxidation state of a metal increases, so does the \_\_\_\_\_\_\_.** **Hardness or Softness**

Answer 33

**Hardness**

Question 34

**The interaction between hard acids and bases can best be described as\_\_\_\_\_\_\_.** **Ionic or Covalent**

Answer 34

**Ionic**

Question 35

**The interaction between soft acids and bases can best be described as\_\_\_\_\_\_\_.** **Ionic or Covalent**

Answer 35

**Covalent**

Question 36

***_Hard-Soft Theory:_*** ***Hard Acids and Bases***

Answer 36

* **Non-polarizable.** * **Typically small and highly charged (Charge Radius Ratio)**

Question 37

**Identify the relationship between the two Cl^- ligands**

Answer 37

## Footnote **Cis**

Question 38

**Identify the relationship between the two Cl^- ligands**

Answer 38

## Footnote **Trans**