复旦大学无机化学IC04.pptVIP

Carbon-silicon Oxide of carbon and silicon is noticeable. CO2 (carbon dioxide) is molecular crystal which is constituted together by van der Waal’s force. SiO2 (silicon dioxide) is atomic crystal which is constituted by Si-O covalent bonds. At special condition, for example, under T 1800 K and P 400,000 atm, quartz-like phase of CO2 (CO2-Ⅴ) can be formed. Its IR spectra and structure are similar to that of quartz (SiO2). Under 350,000-600,000 atm, the properties and structure of carbonate are also similar to silicate. The structure is constituted by corner-sharing and/or edge-sharing of the units of tetrahedral {CO4}. The corner-sharing is that one oxygen atom is shared by two units of {CO4}. The edge-sharing is that two oxygen atoms are shared by two units of {CO4}. The face sharing also exists in some rare structures, at that case three atoms are shared by two units. (2) pπ-pπ Bond The pπ-pπ bond or double bond between carbon, nitrogen or oxygen atoms of the second row are usually observed, such as C=C, C≡C, C=O, C≡N, O=C=O, N=N-O, N=O, etc. For the third row, formation of double bond between silicon, phosphorus or sulfur atoms is difficult. There are two possible reasons for explaining the instability of doubly bonded silicon structure involving pπ-pπ bonds. (i) Overlap of 3pπ-3pπ overlap of 2pπ-2pπ, we can observe the bond energy ordering of pπ-pπ overlap. The bond energy (kJ mol-1) C=C C=Si C=Ge C=Sn Si=Si 272 159 140 79 105 2p-2p 2p-3p 2p-4p 2p-5p 3p-3p As principal quantum number increase, the pπ-pπ overlap reduces. (ii) d Orbital participation may favor two single bonds over the one double bond. If silicon atom is bonded with a big group, the doubly silicon bonded Si=Si compounds may be prepared: X = 2,6-Me2C6H3 The addition reactions can occur over doubly bonded Si=Si: 3. The use of d orbitals by nonmetals The elements Li (lithium) to F (fluorine) are