An understanding of the differences between carbon and silicon is important in understanding the relative chemistry of these Group 14 elements.
As expected silicon is larger than carbon due to the presence of a second shell: i.e., C = 1s2 2s2 2p2 while Si = 1s2 2s2 2p6 3s2 3p2. A comparison of the relative sizes of carbon and silicon are given in Table 1.
| Element | Atomic radius (Å) | Covalent radius sp3 (Å) | van der Waal radius (Å) |
| C | 0.91 | 1.11 | 0.77 |
| Si | 1.46 | 0.76 | 1.17 |
Carbon is known to have a coordination number of 2, 3, and 4 in its compounds depending on the hybridization. A coordination number of 1 can also be considered for CO and CN-. Four-coordinate carbon may be considered to be coordinatively saturated. In contrast, in the absence of overwhelming steric bulk, silicon is observed to have coordination numbers of 3, 4, 5, and 6. Examples of five and six-coordinate silicon include Si(acac)2Cl and SiF62-, respectively. Coordination numbers of higher than 4 have been ascribed to the use of low-lying d orbitals; however, calculations show these are not significant. Instead, hypervalent silicon is better described by the formation of 3-center molecular orbitals, e.g., Figure 1.
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The electronegativities of silicon and carbon are given in Table along with hydrogen. Since carbon is more electronegative than hydrogen the C-H bond is polarized towards carbon resulting in a more protic hydrogen (Figure 2a). In contrast, the lower electronegativity of silicon results in a more hydridic hydrogen (Figure 2b). This difference is reflected in the reaction chemistry of SiH4 versus CH4.
| Element | Pauling scale |
| C | 2.5 |
| H | 2.1 |
| Si | 1.8 |
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The E-E and E-O bond energies for carbon and silicon are given in Table 3. The bond energy for a C-C bond is slightly greater than for a C-O bond, while the Si-O bond is significantly stronger than the Si-Si bond. This difference is reflected in the chemistry of silicon versus carbon compounds. The chemistry of carbon is dominated by catenation: the ability of a chemical element to form a long chain-like structure via a series of covalent bonds. Although silicon does form Si-Si bonds, they are far more reactive than their C-C analogs, and polymers of silicon are predominantly comprised of Si-O chains (as a result of the very strong bond).
| Element | E-E bond energy (kJ/mol) | E-O bond energy (kJ/mol) |
| C | 356 | 335 |
| Si | 230 | 370 |
While unsaturated compounds for carbon (i.e., alkenes and alkynes) are common, the analogous silicon compounds (disilenes) were only reported in 1981, and disilynes in 2004. The Si=Si double bond lengths are 2.14 - 2.29 Å which is 5 - 10% shorter than the Si-Si single bond lengths. This bond shortening is less than ca. 13% in carbon compounds.
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This work is licensed by Andrew R. Barron under a Creative Commons Attribution License (CC-BY 3.0), and is an Open Educational Resource.
Last edited by Andrew R. Barron on Jun 3, 2013 8:52 am -0500.
