Pi backbonding

π backbonding, also called π backdonation, is a concept from chemistry in which electrons move from an atomic orbital on one atom to a π* antibonding orbital on a π-acceptor ligand. It is especially common in the organometallic chemistry of transition metals with multi-atomic ligands such as carbon monoxide, ethylene or the nitrosonium cation. Electrons from the metal are used to bond to the ligand, in the process relieving the metal of excess negative charge. Compounds where π backbonding occurs include Ni(CO)₄ and Zeise's salt. IUPAC offers the following definition for backbonding:

A description of the bonding of π-conjugated ligands to a transition metal which involves a synergic process with donation of electrons from the filled π-orbital or lone electron pair orbital of the ligand into an empty orbital of the metal (donor–acceptor bond), together with release (back donation) of electrons from an nd orbital of the metal (which is of π-symmetry with respect to the metal–ligand axis) into the empty π*-antibonding orbital of the ligand.

The electrons are partially transferred from a d-orbital of the metal to anti-bonding molecular orbitals of CO (and its analogues). This electron-transfer (i) strengthens the metal–C bond and (ii) weakens the C–O bond. The strengthening of the M–CO bond is reflected in increases of the vibrational frequencies for the M–C bond (often outside of the range for the usual IR spectrophotometers). Furthermore, the M–CO bond length is shortened. The weakening of the C–O bond is indicated by a decrease in the wavenumber of the ν_CO band(s) from that for free CO (2143 cm⁻¹), for example to 2060 cm⁻¹ in Ni(CO)₄ and 1981 cm⁻¹ in Cr(CO)₆, and 1790 cm⁻¹ in the anion [Fe(CO)₄]²⁻. For this reason, IR spectroscopy is an important diagnostic technique in metal–carbonyl chemistry. The article infrared spectroscopy of metal carbonyls discusses this in detail.

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