Inorganic Chemistry, carbonyl ligand longer weaker two文档.pdfVIP

- 54 - EXPERIMENT 7 - METAL CARBONYLS References J. E. Huheey, Inorganic Chemistry, 3rd Edition, pages 139-42, 363-67, 589-610. FA. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 4th Edition, pages 433-436. Shriver, Atkins, and Langford, Inorganic Chemistry sections 16.3-5. Housecroft, C. E., Sharpe, A. G., Inorganic Chemistry, pp. 585 – 592. Background Carbon monoxide (CO) is a colorless, odorless, flammable, highly toxic gas and is isoelectronic with dinitrogen (N - 2) and the cyanide anion (CN ). It is capable of forming complexes with metal ions that are in a low oxidation state (usually -2 to +2) and is then known as a carbonyl ligand. It is usually found that the C-O bond is longer and weaker in a carbonyl ligand than in gaseous carbon monoxide. To understand the way in which CO attaches itself to a metal ion we must first understand the bonding between the carbon and oxygen atoms. These atoms are held together by a σ bond, formed by the overlap of the carbon and oxygen 2pz orbitals, shown here, and two π - - + + - + - σ-bond formation bonds (one of which is shown on the following page). Electrons in these orbitals are more likely to be found at the oxygen end of the molecule (oxygen is the more electronegative atom) and so the orbital lobes are drawn somewhat lopsided to indicate this polarization. One π bond is the result of overlap of the C 2p with the O 2p atomic orbitals, and the second of th