Abstract
Recently, some works have focused attention on the reactivity of silicon atom with closed-shell molecules. Silicon may form a few relatively stable compounds with CO, i.e. Si(CO), Si(CO)2, Si[C2O2], while the existence of polycarbonyl (n>2) silicon complexes has been rejected by current literature. In this paper, the reaction of silicon with carbonyl has been reinvestigated by density functional calculations. It has been found that the tetracoordinated planar Si(CO)4 complex is thermodynamically stable. In Si(CO), silicon carbonyl, and Si(CO)2, silicon dicarbonyl, the CO are datively bonded to Si; Si(CO)4, silicon tetracarbonyl, may be viewed as a resonance between the extreme configurations (CO)2Si + 2CO and 2CO + Si(CO)2; while Si[C2O2], c-silicodiketone, is similar to the compounds formed by silicon and ethylene. A detailed orbital analysis has shown that the Si bonding with two CO is consistent with the use of sp 2-hybridized orbitals on silicon, while the Si bonding with four CO is consistent with the use of sp 2 d-hybridized orbitals on silicon, giving rise to a planar structure about Si.
Similar content being viewed by others
References
Kageshima H, Shiraishi K (1998). Phys Rev Lett 81:5936
Kageshima H, Shiraishi K, Uematsu M (1999). Jpn J Appl Phys 38:L971
Belanzoni P, Giorgi G, Cerofolini GF (2004). Chem Phys Lett 400:179
Belanzoni P, Giorgi G, Cerofolini GF, Sgamellotti A (2005). Inorg Chem 44:1381
Cerofolini GF, Belanzoni P, Giorgi G, Sgamellotti A (2005). Appl Phys A 80:1617
Su MD, Amos RD, Handy NC (1990). J Am Chem Soc 112:1499
Talbi D (2005). Chem Phys 313:17
Bu Y, Cao Z (2002). Theor Chem Acc 108:293
Cai Z-L, Wang Y-F, Xiao H-M (1992). Chem Phys Lett 191:533
DeKock RL, Grev RS, Schaefer HF III (1988). J Chem Phys 89:3016
Lembke RR, Ferrante RF, Weltner W Jr (1977). J Am Chem Soc 99:416
Stolvik R (1985). J Mol Struct 124:133
Baerends EJ, Ellis DE, Ros P (1973). Chem Phys 2:42
ADF2002.01 SCM Theoretical Chemistry Vrije Universiteit Amsterdam The Netherlands http://www.scm.com
te Velde G, Bickelhaupt FM, van Gisbergen SJA, Fonseca Baerends EJ, Snijders JG, Ziegler T (2001). J Comput Chem 22:931
Fonseca Guerra C, Snijders JG, te Velde G, Baerends EJ (1998). Theor Chem Acc 99:391
te Velde G, Baerends EJ (1992). J Comput Phys 99:84
Ceperley DM, Alder BJ (1980). Phys Rev Lett 45:566
Vosko SH, Wilk L, Nusair M (1980). Can J Phys 58:1200
Becke AD (1988). Phys Rev A 38:3098
Perdew JP (1986). Phys Rev B 33:8822
Perdew JP (1986). Phys Rev B 34:7406
Morokuma K (1971). J Chem Phys 55:1236
Kitaura K, Morokuma K (1976). Int J Quantum Chem 10:325
Ziegler T, Rauk A (1977). Theor Chim Acta 46:1
Baerends EJ, Branchadell V, Sodupe M (1997). Chem Phys Lett 265:481
Meyer H, Nagorsen G (1979). Angew Chem Int Ed Engl 18:551
Schomburg D (1983). Angew Chem Int Ed Engl 22:65
Würthwein E-U, Schleyer PvR (1979). Angew Chem Int Ed Engl 18:553
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Belanzoni, P., Giorgi, G., Cerofolini, G.F. et al. The Silicon Carbonyls Revisited: On the Existence of a Planar Si(CO)4 . Theor Chem Acc 115, 448–459 (2006). https://doi.org/10.1007/s00214-006-0127-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00214-006-0127-z