What is an innocent ligand vs. a non-innocent ligand?
1 Answer
An innocent ligand is one that binds to a transition metal in such a way that the oxidation state of the metal is able to be determined with clarity, i.e. the method of binding and the contributed charge are both unambiguous.
On the other hand, a non-innocent ligand can bind in multiple ways in which the contributed charge must be stated first before being able to determine the oxidation state of a transition metal with clarity.
Some examples of innocent ligands:
- acetylacetonato (a bidentate that bonds via the
#pi# system established by the two oxygens) - ammine (
#"NH"_2# ) (simple monodentate ligand) - ethylenediamine (
#"H"_2"N"-("CH"_2)_2-"NH"_2# ; cis) (bidentate ligand that binds in a similar way to the ammine ligand)
Some examples of non-innocent ligands:
- Nitrosyl (
#"NO"^(+)# vs.#"NO"^(-)# ) - Dioxo (
#"O"_2^(-)# vs.#"O"_2^(2-)# ) - Dithiolene (three different possible bonding modes!!!)
For the rest of this answer I go into more depth on the nitrosyl ligand, which is apparently "simple" (at least, according to Jørgensen).
THE NITROSYL LIGAND IS "NON-INNOCENT"
A "simple" example of a non-innocent ligand that we can go more in-depth on is the nitrosyl ligand, which can either bind as
Two examples that illustrate a difference in bonding mode for the nitrosyl ligand are:
#\mathbf(["Co"("en")_2("NO")"Cl"]^(+))# (with a bent nitrosyl)#\mathbf(["Fe"("CN")_5("NO")]^(3-))# (with a linear nitrosyl).
One of the isomers for each compound are shown below.
In the iron compound, we have five
So, we have accounted for an
#"NO"^(+)# , linear, bonding mode. FYI, iron in this case is a#d^7# metal. For this compound we have#6# #pi# -compatible (#t_(2g)# ) electrons, and the oxidation state of the metal is#color(blue)(+1)# .
In the cobalt compound, we have
So, we have accounted for an
#"NO"^(-)# , bent, bonding mode. FYI, cobalt in this case is a#d^6# metal. For this compound we have#7# #pi# -compatible (#t_(2g)# ) electrons, and the oxidation state of the metal is#color(blue)(+3)# .
Not the same oxidation state for the metal atom!
According to the Enemark-Feltham approach, the
WHY THE DIFFERENCE IN BONDING MODE FAVORABILITY?
If you're curious, the difference in the bonding modes can be explained by the extent of
This is a stabilizing interaction between the compatible metal
LINEAR NITROSYL
Basically,
If we take the plane of the screen to be the
A similar
BENT NITROSYL
On the other hand,
They are compatible with only the
So, we have the issue that the nitrogen contributes no
As a result, electron density cannot be donated into the
Usually textbooks will specify which bonding mode they want to use for a given non-innocent ligand; mine specifies