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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 ''n''d orbital of the metal (which is of π-symmetry with respect to the metal–ligand axis) into the empty π ==Metal carbonyls, nitrosyls, and isocyanides== 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-C''O 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), 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 ()2−.〔Housecroft C.E. and Sharpe A.G. ''Inorganic Chemistry'' (2nd ed. Pearson Prentice-Hall 2005) p.702. ISBN 0130-39913-2〕 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. 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. Isocyanides, RNC, are another class of ligands that are able of π-backbonding. In contrast with CO, the σ-donor lone pair on the C atom of isocyanides is antibonding in nature and upon complexation the CN bond is strengthened and the νCN increased. At the same time, π-backbonding lowers the νCN. Depending on the balance of σ-bonding versus π-backbonding, the νCN can either be raised (for example, upon complexation with weak π-donor metals, such as Pt(II)) or lowered (for example, upon complexation with strong π-donor metals, such as Ni(0)). 〔Robert H. Crabtree ''The Organometallic Chemistry of the Transition Metals'' (6th ed. Wiley 2014) p. 105-106. ISBN 9781118138076〕 For the isocyanides, an additional parameter is the M''C=N-C'' angle, which deviates from 180° in highly electron-rich systems. Other ligands have weak π-backbonding abilities, which creates a labilization effect of CO, which is described by the cis effect. 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「pi backbonding」の詳細全文を読む スポンサード リンク
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