Carbon monoxide bonds to transition metals using "synergistic pi* back-bonding". The M-C bonding has three components, giving rise to a partial triple bond. A sigma (σ) bond arises from overlap of the nonbonding (or weakly anti-bonding) sp-hybridized electron pair on carbon with a blend of d-, s-, and p-orbitals on the metal. A pair of pi (π) bonds arises from overlap of filled d-orbitals on the metal with a pair of π*-antibonding orbitals projecting from the carbon atom of the CO. The latter kind of binding requires that the metal have d-electrons, and that the metal is in a relatively low oxidation state (0 or +1) which makes the back-donation of electron density favorable. As electrons from the metal fill the π-antibonding orbital of CO, they weaken the carbon–oxygen bond compared with free carbon monoxide, while the metal–carbon bond is strengthened. Because of the multiple bond character of the M–CO linkage, the distance between the metal and carbon atom is relatively short, often less than 1.8 Å, about 0.2 Å shorter than a metal–alkyl bond.  The M-CO and MC-O distance are sensitive to other ligands on the metal. Illustrative of these effects are the following data for Mo-C and C-O distances in Mo(CO) and Mo(CO)(4-methylpyridine): 2.06 vs 1.90 and 1.11 vs 1.18 Å.
Infrared spectroscopy is a sensitive probe for the presence of bridging carbonyl ligands. For compounds with doubly bridging CO ligands, denoted μ-CO or often just μ-CO, the bond stretching frequency ν is usually shifted by 100–200 cm to lower energy compared to the signatures of terminal CO, which are in the region 1800 cm. Bands for face capping (μ) CO ligands appear at even lower energies. In addition to symmetrical bridging modes, CO can be found to bridge asymmetrically or through donation from a metal d orbital to the π* orbital of CO. The increased π-bonding due to back-donation from multiple metal centers results in further weakening of the C–O bond.