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 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. [Fe(CO)₄]²⁻ + HCl → [HFe(CO)₄]⁻ + Cl⁻

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.

Simple alkyl ligands

A simple alkyl ligand forms an M―C single bond, and in doing so the alkyl group acts as a one-electron monohapto ligand. Many such compounds are known, but they are less common in the d block than in the s and p blocks. This may in part be a result of the modest M―C bond strengths. Another reason for the limited stability of alkyl ligands in many d-block complexes is a set of reactions that can be quite rapid, such as β-hydrogen elimination, CO insertion, and reductive elimination. As described below, these reactions transform simple hydrocarbon ligands into other groups.

The β-hydrogen elimination reaction is an important feature of the hydrocarbon chemistry of both d- and p-block organometallics. The reaction consists of the abstraction of a hydrogen atom from the organic ligand with the formation of two products, one of which contains a metal-hydrogen bond and the other of which is an alkene. L_nM―CH₂CH₃ → L_nM―H + H₂C=CH₂ (L_n represents the n ligands not involved in the hydrogen elimination.) The reverse of this reaction, alkene insertion into the M―H bond, is illustrated by the hydroboration and hydrosilation reactions discussed above. Both the β-hydrogen elimination and addition of M―H across a C=C double bond are thought to proceed through a cyclic intermediate involving a three-centre, two-electron bond where a hydrogen atom bridges between the carbon and the metal atoms.

Since a compound with no hydrogen atoms on the β-carbon atom cannot undergo β-hydrogen elimination, benzyl, CH₂(C₆H₅), and methyltrimethylsilyl, CH₂Si(CH₃)₃ (shown below) ligands are generally more robust than ethyl ligands when attached to d-block metal atoms. Similarly, the lack of β-hydrogen atoms on the methyl group accounts for the greater stability of complexes containing the methyl ligand rather than the ethyl ligand.

A reaction frequently referred to as CO insertion leads to carbon-carbon bond formation between the carbon atom of a carbonyl ligand and the carbon atom of an alkyl ligand, which is the methyl group in the following example.

The CO insertion reaction is involved in all the transformations of [Fe(CO)₄R]⁻ into organic molecules.

Another type of reaction that can transform an attached organic ligand (as well as other groups) is reductive elimination.

The converse of reductive elimination is oxidative addition.

The reactions discussed above, insertion of C=C into an M―H bond, β-hydrogen elimination, and CO insertion, are often employed for the synthesis of organic molecules in the laboratory and in industry. They also account for some of the individual steps in some important catalytic cycles (see below Organometallic compounds in catalysis).

Alkylidene ligands

Alkylidene ligands, such as CH₂, CHR, or CR₂, form the M=C d-p double bonds (i.e., bonds between the d orbitals of the metal and the p orbitals of the carbon), and their metal compounds are often called carbenes. The first stable metal carbene complex was discovered in the laboratory of the German chemist Ernst O. Fischer in Munich by the reaction of a metal carbonyl with an alkyllithium compound. In this reaction, the alkyl group is transferred (as an R⁻ group) to the carbon atom of the coordinated carbonyl, and subsequent addition of carbocation reagent results in attachment of an R⁺ group to the oxygen.

This type of carbene complex is common for the atoms of metals in groups 6–8, and they are called Fischer carbenes. The Fischer carbenes can be modified by electron-rich groups. For example, the attack of an amine on the electron-poor carbon atom of a Fischer carbene results in the displacement of the OR group to yield a new carbene (Me represents the methyl group, ―CH₃).

The attack of an electron-rich amine (indicated by δ- in the above equation) on the carbon atom in the Fischer carbene is attributed to the significant electronegativity of the middle to late d-block metals, which makes the carbon atom of the carbene electron-poor (indicated by δ+ in the above equation).

The reactions of Fischer carbene complexes with alkynes has considerable utility in organic synthesis. For example, naphthyl compounds (i.e., those derived from the fused ring system C₁₀H₈) can be synthesized by the reaction of methoxy phenyl Fischer carbenes with an alkyne.

The chromium can be removed from the organic product by mild oxidation. Another route to a carbene is the deprotonation of an alkyl ligand, producing a carbene that contains only hydrocarbon ligands.

These ligands that contain only carbon and hydrogen are commonly attached to metal atoms from the early part of the d block such as titanium (Ti) and tantalum (Ta). The complexes are known as Schrock carbenes for their discoverer, American chemist Richard Schrock. The chemistry and spectroscopy of the Schrock carbenes indicate that these compounds have the opposite polarity of the Fischer carbenes. The carbon behaves as if it were electron-rich, because the M^δ+=C^δ− bond is polarized so as to put negative charge on the metal-bound carbon, for the early d-block metals readily give up electrons. As a result, the carbon attached to the metal atom in a Schrock carbene reacts with electron-seeking reagents, such as Me₃Si^δ+Br^δ+, at the carbene carbon (Cp is a common abbreviation for the cyclopentadienyl ligand, ―C₅H₅).

An interesting reaction of the Schrock carbenes is the alkene metathesis reaction:

This reaction appears to proceed through a four-membered ring intermediate containing carbon atoms and the metal atom.

Alkylidyne ligands

Alkylidyne ligands have the general formula CH or CR. They are bound to the metal by an M≡C triple bond involving one σ bond and two d-p π bonds. The simplest member of this series is methylidyne, CH, and the next simplest, CCH₃, is ethylidyne. One route to methylidynes, discovered in Fischer’s laboratory, involves the abstraction of an alkoxide group (OR) from a Fischer carbene by BBr₃.