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* anti-bonding orbital on another atom or ligand.[1][2] 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.[3]
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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 frequency of the νCO band(s) from that for free CO (2143 cm-1) often by more than 200 cm-1. For this reason, IR spectroscopy is an important diagnostic technique in metal-carbonyl chemistry.
Many ligands other than CO are strong "backbonders". Nitric oxide is an even stronger π-acceptor than is CO and νNO is a diagnostic tool in metal-nitrosyl chemistry. In the case of isocyanide complexes, the degree of π-bonding is again indicated by shortening of the M-CNR bond and by decrease in νCN. For the isocyanides however, an additional parameter is the MC=N-C angle, which deviates form 180° in highly electron-rich systems.
As in metal-carbonyls, electrons are partially transferred from a d-orbital of the metal to anti-bonding molecular orbitals of the alkenes and alkynes. This electron-transfer (i) strengthens the metal-ligand bond and (ii) weakens the C-C bonds within the ligand. In the case of metal-alkenes and alkynes, the strengthening of the M-C2R4 and M-C2R2 bond is reflected in bending of the C-C-R angles which assume greater sp3 and sp2 character, respectively. Thus strong pi-backbonding causes a metal-alkene complex to assume the character of a metallacyclopropane. Electronegative substituents greater pi backbonding. Thus strong pi backbonding ligands are tetrafluoroethylene, tetracyanoethylene, and hexafluoro-2-butyne.
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