Coordination Chemistry Flashcards
This type of associativemechanism where no intermediate is formed and the rate does depends on the nature of the entering group.
Associative interchange mechanism
Bonding-making is more important than bond-breaking.
The dissociative mechanism where no intermediate is formed and the rate does not depends on the nature of the entering group.
Dissociative interchange mechanism
Bonding-breaking is more important than bond-making.
Idenfity the mechanism below.
Dissociative mechanism
The rate depends on breaking the bond of the leaving group.
Idenfity the mechanism below.
Associative mechanism
The rate depends on the properties of the entering group and the encounter complex (intermediate)
As the size of the leaving group increases, the rate of a associative mechanism ________.
Increases, Decreases, or No effect
No effect
As the size of the entering group increases, the rate of an associative mechanism ________.
Increases, Decreases, or No effect
- *Decreases
- (Associative mechanisms are sensitive to the entering group and larger ligands tend to form unfavorable steric interactions with bound ligands)***
As the size of the entering group increases, the rate of a dissociative mechanism ________.
Increases, Decreases, or No effect
No effect
(The rate determining step in a dissociative mechanism is breaking the metal-ligand bond)
As the size of the metal increases, the rate of an associative mechanism ________.
Increases, Decreases, or No effect
Increases
(Large Coordination sphere favors associative mechanism )
As the size of the metal increases, the rate of a dissociative mechanism ________.
Increases, Decreases, or No effect
Increases
As the charge increases on the entering group, the rate of an associative mechanism ________.
Increases, Decreases, or No effect
Increases
As the charge increases on the entering group, the rate of a dissociative mechanism ________.
Increases, Decreases, or No effect
No effect
(The rate determining step in a dissociative mechanism is breaking the metal-ligand bond)
As the negative charge increases on the leaving group, the rate of an associative mechanism ________.
Increases, Decreases, or No effect
Decreases
As the neagtive charge increases on the leaving group, the rate of a dissociative mechanism ________.
Increases, Decreases, or No effect
Decreases
As the charge increases on the metal center, the rate of an associative mechanism ________.
Increases, Decreases, or No effect
Increases
As the charge increases on the metal center, the rate of a dissociative mechanism ________.
Increases, Decreases, or No effect
Decreases
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
Increases
Jahn-Teller ions have __________ water exchange rates.
Fast or Slow
Fast
In what order should dimethyl sulfide and pyridine be adding to AuI4- below?
Dimethyl sulfide is more trans directing than iodine and pyridine
What would be the Rh product of the reaction between [Rh(Cl)3(CO)]- and 1 eqv. PPh3?
trans-[Rh(Cl)2(CO)(PPh3)]-
Substitution occurs trans to the
strongest trans effect ligand CO > Cl-
Refers to the impact of a ligand on the strength of the bond trans to it in the ground state of a complex.
Trans influence (Structrual trans effect)
Ground State Property
Refers to the impact of a ligand on the length of the bond trans to it in the ground state of a complex.
Trans influence (Structrual trans effect)
Ground State Property
Chelate ligands form much more stable metal complexes than monodentate ligands.
Chelate Effect
Refers to the observation that certain ligands increase the rate of ligand substitution when positioned trans to the departing ligand
Trans Effect [kinetic trans effect]
Both σ-donors and/or π-donors
As the M-X bond strength increases, the rate of dissociative mechanism _____.
Increases or Decreases
Decreases
The rate determining step involves bond breaking
Hard-Soft Theory:
Soft Acids and Bases
- Highly polarizable
- Typically large and low charge
The energy difference between the ground state CFSE and the transition state CFSE.
Crystal Field Activation Energy (CFAE)
The stability that results from placing a transition metal ion in the crystal field generated by a set of point charges.
Crystal Field Stabilization Energy
(CFSE)
What nomenclature is the best description for the adduct below.
Side-on η2 peroxo
η2- two oxygen atoms chelates side-on
What nomenclature is the best description of the adduct below.
Side-on η2 superoxo
η2- two oxygen atoms
What nomenclature is the best description of the adduct below.
Bis-(μ-oxo)
Bis-two oxygen atoms
μ-bridging
Identify the best description of the O2 adduct below.
μ-η2 : η2 peroxo
- μ-bridging*
- η2-both oxygen coordinated*
Identify the best description of the O2 adduct below.
Peroxo
As the oxidation state of a metal increases, so does the _______.
Hardness or Softness
Hardness
The interaction between hard acids and bases can best be described as_______.
Ionic or Covalent
Ionic
The interaction between soft acids and bases can best be described as_______.
Ionic or Covalent
Covalent
Hard-Soft Theory:
Hard Acids and Bases
- Non-polarizable.
- Typically small and highly charged (Charge Radius Ratio)
Identify the relationship between the two Cl- ligands
Cis
Identify the relationship between the two Cl- ligands
Trans
