第一周 金属有机导论及锂、钠、钾有机化合物.pptVIP

Definition Defination of Organometallic chemistry Compounds containing metal-carbon bonds（M?+?C??） Exist at ordinary temperatures as low melting crystals, liquids or gases Commonly soluble in weakly polar organic solvents eg. toluene, ethers, alcohols Variable chemical properties Based on type of metal-carbon bond Ionic – most electropositive elements Covalent – electron deficient: metals with less than half filled valency shells, form strongly polarizing cations – electron precise – electron rich Ionic Ionic – M+R- highly electropositive metals very reactive high mpt. low volatility Low or negligible solubilities in non-polar, non coordinating solvents Highly polar covalent Highly polar, covalent – Li, Al alkyls, Grignard reagents Polarity is a source of reactivity Adopt associated structures Slightly polar covalent Slightly polar covalent – less electropositive elements Behave like organic compounds Low mpt. Volatile Soluble in non-polar solvents Stability of OrganometallicCompounds Oxidation All organometallic compounds are thermodynamically unstable to oxidation (stable or unstable) – Due to large negative free energies of formation of metal oxide, carbon dioxide and water Many kinetically unstable to oxidation at or below room temperature (inert or labile) – Associated with the presence of empty low lying orbitals on the metal atom, or a non bonding pair of electrons Hydrolysis Involves nucleophilic attack by water Facilitated by the presence of empty low lying orbitals on the metal atom which can accept electrons – Organometallic compounds of Gps 1, 2, Zn, Cd, Al, Ga, In readily hydrolysed Rate of hydrolysis is dependent on M-C bond polarity – greater polarity, faster rate Alkyls and Aryls of groups 14 and 15 are kinetically inert to hydrolysis by water because the metal atoms are surrounded by a filled shell of 8 electrons. Nucleophilic attack is no longer favored