Organometallic Chemistry

Metal Carbonyl Anions

More remarkable than the formation of zero-oxidation-state metal

carbonyls is the reduction of many of these carbonyl compounds to
metal carbonyl anions, in which the metal has a negative oxidation
state. The following example demonstrates that the two-electron
reduction by sodium metal is accompanied by the loss of the two-
electron donor carbonyl ligand, and so the 18-electron count on
iron is preserved; the solvent is tetrahydrofuran (THF).
The organometallic reagent Fe(CO)42− can undergo multiple
reactions in the synthesis of organic molecules
 W C Zeise, Danish
pharmacist, I789- I847 The stabilization of very electron-rich complexes, such as [Fe(CO)4]2-, is
attributed to the back π bonding that shifts electron density from the metal
to the carbonyl ligands, and this view is substantiated by C-O bond
distances and other physical data. The metal atom in these carbonyl
anions is assigned a negative oxidation state (2- in the above example).
This formalism does not acknowledge the delocalization of electron density
from the metal to the ligand, but the chemical properties of the carbonyl
anions do suggest that some of the negative charge resides on the metal.
For example, a metal carbonyl anion can be protonated with the H+ ion,
which generally attaches to the central metal and not a carbonyl ligand, as
in the following example.
 W C Zeise, Danish
pharmacist, I789- I847 Owing to their high reactivity, carbonyl anions are useful
starting materials for the synthesis of other organometallic
compounds, and this accounts for their applications in
organic synthesis. For example, [Fe(CO)4]2- is used to extend a
carbon chain by transfer of the carbonyl substituent,
producing aldehydes, ketones, or carboxylic acids.
 18 Electron Rule: How to count electrons?

The rule states that thermodynamically stable transition metal

organometallic compounds are formed when the sum of the metal d
electrons and the electrons conventionally considered as being supplied
by the surrounding ligands equals 18.
In general, the conditions favoring adherence to the 18 electron rule are,
Edward Frankland
an electron rich metal (one that is in a low oxidation state) and ligands
1825-1899
that are good π‐acceptors. The hapto symbol, η, with a numerical
Frankland coined the
term superscript, provides a topological description by indicating the
“Organometallic” connectivity between the ligand and the central atom. For example, if all
the five carbon atoms of a cyclopentadienyl moiety are equidistant from
a metal atom, we term it as η5‐cyclopentadienyl. The Hapticity of the
ligand (η) is the number of ligand atoms bound to the metal.
Examples:
1-R, 1-Ar 2-C2R4 1-allyl, 3-allyl, 4- Cb, 5-Cp, 6-C6H6 8-
C8H8 2-C60, 5-R5C60.
The symbol  indicates bridging normally we have 2 and rarely 3 bridging

Examples:
2-CO, 3-CO, 2-CH3, 2-H, 2-Cl, , 3-Cl, 2-OR, 2-PR2, 2-NR2

(A) Ionic model (Donor pair method)

 Ligands donate electrons.
 The charge on ligands must be known.
 Oxidation state must be known or must know metal to comply with 18 electron rule.
(B) Covalent model (Neutral ligand method).
 Don’t need oxidation state.
 Don’t need a charge.
 Positive ligands donate one more under (A) and negative ligands donate one less under (B),
when counting with A and B method
 Methods of counting: Neutral atom method & Oxidation state method

Ligand Neutral Oxidation state Ligand Neutral Oxidation state

atom atom
Electron Formal Electron Formal
contributi charge contribu charge
on tion
Carbonyl (M–CO) 2 2 0 Halogen ( M–X) 1 2 –1
Phosphine (M–PR3) 2 2 0 Alkyl (M–R) 1 2 –1
Amine (M–NR3 ) 2 2 0 Aryl (M–Ar) 1 2 –1
Amide (M–NR2 ) 1 2 –1 acyl (M–C(O)–R 1 2 –1
Hydrogen (M–H) 1 2 –1 1-cyclopentadienyl 1 2 –1
Alkene (sidewise) 2- 2 2 0 1-allyl 1 2 –1
Alkyne (sidewise)  2- 2 2 0 3-allyl 3 4 –1
2-C60 2 2 0 5-cyclopentadienyl 5 6 –1
Nitrosyl bent 1 2 –1 6-benzene 6 6 0
Nitrosyl linear 3 2 +1 7-cycloheptatrienyl 7 6 +1
Carbene (M=CR2) 2 4 –2 Carbyne (MCR) 3 6 –3
Alkoxide (M–OR) 1 2 –1 Thiolate (M–SR) 1 2 –1
-CO (M–(CO)–M) 2 2 0 -H 1 2 –1
-alkyne 4 4 0 -X (M–X–M) 3 4 –1
X = halogen
-alkyl 1 2 –1 -amido 3 4 –1
(M–(NR2)–M
-phosphido 3 4 –1 -alkoxide 3 4 –1
(M–(PR2)–M (M–(OR)–M
 neutral atom oxidation state
method method
CO Ru 8 6 (Ru +2)
PPh3
Ru 3- allyl 3 4
2 PPh3 4 4
PPh3
CO 2 2
charge -1 not required
16 16
Me
N Fe 8 6 (Fe +2)
Me
Fe 2 5-Cp 10 12
18 18

Neutral atom method: Metal is taken as in zero oxidation state for counting purpose

Oxidation state method: We first arrive at the oxidation state of the metal by considering the
number of anionic ligands present and overall charge of the complex

Suggestion: Focus on one counting method till you are confident