Coordination Chemistry Flashcards

1
Q

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

A

Associative interchange mechanism

Bonding-making is more important than bond-breaking.

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2
Q

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

A

Dissociative interchange mechanism

Bonding-breaking is more important than bond-making.

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3
Q

Idenfity the mechanism below.

A

Dissociative mechanism

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

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4
Q

Idenfity the mechanism below.

A

Associative mechanism

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

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5
Q

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

Increases, Decreases, or No effect

A

No effect

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6
Q

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

Increases, Decreases, or No effect

A
  • *Decreases
  • (Associative mechanisms are sensitive to the entering group and larger ligands tend to form unfavorable steric interactions with bound ligands)***
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7
Q

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

Increases, Decreases, or No effect

A

No effect

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

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8
Q

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

Increases, Decreases, or No effect

A

Increases

(Large Coordination sphere favors associative mechanism )

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9
Q

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

Increases, Decreases, or No effect

A

Increases

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10
Q

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

Increases, Decreases, or No effect ​

A

Increases

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11
Q

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

Increases, Decreases, or No effect ​

A

No effect

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

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12
Q

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

Increases, Decreases, or No effect ​

A

Decreases

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13
Q

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

Increases, Decreases, or No effect ​

A

Decreases

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14
Q

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

Increases, Decreases, or No effect ​

A

Increases

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15
Q

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

Increases, Decreases, or No effect ​

A

Decreases

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16
Q

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

A

Increases

17
Q

Jahn-Teller ions have __________ water exchange rates.

Fast or Slow

A

Fast

18
Q

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

A

Dimethyl sulfide is more trans directing than iodine and pyridine

19
Q

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

A

trans-[Rh(Cl)2(CO)(PPh3)]-

Substitution occurs trans to the

strongest trans effect ligand CO > Cl-

20
Q

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

A

Trans influence (Structrual trans effect)

Ground State Property

21
Q

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

A

Trans influence (Structrual trans effect)

Ground State Property

22
Q

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

A

Chelate Effect

23
Q

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

A

Trans Effect [kinetic trans effect]

Both σ-donors and/or π-donors

24
Q

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

Increases or Decreases

A

Decreases

The rate determining step involves bond breaking

25
Q

Hard-Soft Theory:

Soft Acids and Bases

A
  • Highly polarizable
  • Typically large and low charge
26
Q

The energy difference between the ground state CFSE and the transition state CFSE.

A

Crystal Field Activation Energy (CFAE)

27
Q

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

A

Crystal Field Stabilization Energy

(CFSE)

28
Q

What nomenclature is the best description for the adduct below.

A

Side-on η2 peroxo

η2- two oxygen atoms chelates side-on

29
Q

What nomenclature is the best description of the adduct below.

A

Side-on η2 superoxo

η2- two oxygen atoms

30
Q

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

A

Bis-(μ-oxo)

Bis-two oxygen atoms

μ-bridging

31
Q

Identify the best description of the O2 adduct below.

A

μ-η2 : η2 peroxo

  • μ-bridging*
  • η2-both oxygen coordinated*
32
Q

Identify the best description of the O2 adduct below.

A

Peroxo

33
Q

As the oxidation state of a metal increases, so does the _______.

Hardness or Softness

A

Hardness

34
Q

The interaction between hard acids and bases can best be described as_______.

Ionic or Covalent

A

Ionic

35
Q

The interaction between soft acids and bases can best be described as_______.

Ionic or Covalent

A

Covalent

36
Q

Hard-Soft Theory:

Hard Acids and Bases

A
  • Non-polarizable.
  • Typically small and highly charged (Charge Radius Ratio)
37
Q

Identify the relationship between the two Cl- ligands

A

Cis

38
Q

Identify the relationship between the two Cl- ligands

A

Trans