Boise State University - Summer 2022
Marketing 239, Chapter 7 Essay
Professor Gadson, Section 4
September 21, 2022
In chemistry, reactions that involve a change in spin state are known as spin-forbidden
reactions Such reactions show increased activation energy when compared to a similar
reaction in which the spin states of the reactant and product are isomorphic. As a result of
this increased activation energy, a decreased rate of reaction is observed. (Johnson, 2020)
Class Date: 10/5/2024
Teacher’s Feedback: The introduction could be more engaging.
GENERIC CONTENT:
## Conclusion (List)
- A famous example of spin-forbidden reaction is the very slow reaction of O2 with
hydrocarbons.
- == Examples ==
The dissociation of nitrous oxide is a well-studied process:
N2O → N2 + O
O atoms have a triplet ground state.
## Analysis
Methoxy cation has a triplet ground state. In a mass spectrometer, it dissociates into singlet
products (formyl cation and H2):
CH3O+ → H2 + HCO+
Numerous spin-forbidden reactions are encountered in transition metal chemistry since
many metal ions can adopt multiple spin states. For example, ferrous porphyrin complexes
containing one axial donor are high spin ferrous.
## Findings
These complexes, which are represented by myoglobin and hemoglobin, bind CO to give
singlet products:
Fe(porphyrin)L + CO → OC−Fe(porphyrin)L
Cobalt(I) dicarbonyl complexes of a trispyrazolylborate are diamagnetic. The corresponding
monocarbonyls have triplet ground states. The addition of CO to Fe(CO)4 is an example
showing the slowing effect of spin-forbidden reaction takes place when Fe(CO)x is placed
under CO pressure.
## Discussion
Fe(CO)4 + CO → Fe(CO)5
== Changing spin states ==
When a reaction converts a metal from a singlet to triplet state (or vice versa):
The energy of the two spin states must be nearly equal, as dictated by temperature,
A mechanism is required to change spin states. Strong spin-orbital coupling can satisfy the
2nd condition. Parameter 1, however, can lead to very slow reactions due to large
disparities between the metal complex's potential energy surfaces, which only cross at high
energy leading to a substantial activation barrier. Spin-forbidden reactions formally fall into
the category of electronically non-adiabatic reactions. In general, potential energy surfaces
fall into either the adiabatic and diabatic classification.
## Background
Potential Energy Surfaces that are adiabatic rely on the use of the full electronic
Hamiltonian, which includes the spin-orbit term. Those that are diabatic are likewise
derived by solving the eigenvalues of the Schrödinger equation, but in this case one or more
terms are omitted. === Non-adiabatic transition ===
Once a minimum energy crossing point is reached and parameter 1 above is satisfied, the
system needs to hop from one diabatic surface to the other, as stated above by parameter 2.
At a given energy (E), the rate coefficient [k(E)] of a spin-forbidden reaction can be
calculated using the density of rovibrational states of the reactant [ρ(E)] and the effective
integrated density of states in the crossing seam between the two surfaces [Ner(E)].
## Conclusion
(
E
{\displaystyle k(E)=N_{cr}(E)/hp(E)}
where
d
E
p
s
{\displaystyle N_{cr}(E)=\int dE_{h}\rho _{cr}(E-E_{h})p_{sh}(E_{h})}
The probability of hopping (psh) is calculated from Landau-Zener theory giving
p
s
P
L
{\displaystyle p_{sh}(E)=(1-P_{LZ})(1+P_{LZ})}
where
exp
12
F
μ
{\displaystyle P_{LZ}=\exp \left({\frac {-2\pi H_{12}^{2}}{n\Delta F}}{\sqrt {\frac {\
mu }{2E}}}\right)}
in which the spin-orbit coupling derived off the diagonal Hamiltonian matrix element
between two electronic states (H12), the relative slope of the two surfaces at the crossing
seam [F(Δ)], the reduced mass of the system through its movement along the hopping
coordinate (μ), and the kinetic energy of the system passing through the crossing point (E)
are used. It is useful to note that when Eh < Ec (when below the minimum energy crossing
point) the probability of hopping between spin states is null. == Application to catalysis ==
=== C-H activation ===
Insertion into C-H bonds, known as C-H activation, is an integral first step in C-H
functionalization.
## Analysis
For some metal complexes with identical ligands, C-H activation is rapid when one metal is
used and slow when other metals are used, often first row transition metals, due to the spin
allowed nature of the former case and the spin-forbidden nature of the latter case. The
difference in rates of C-H activation of methane for CoCp(CO), RhCp(CO), and IrCp(CO)
readily demonstrate this property.
References / Works Cited:
1. Wikipedia (n.d.). Retrieved from [Link]
2. Random Book Title (2022). Academic Publishing House.
