A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

Jackson, P., Srinivas, R., Blanksby, Stephen J., Schroder, D., & Schwarz, H. (2000) A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface. Chemistry-a European Journal, 6(7), pp. 1236-1242.

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Abstract

The cation[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected [Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated [Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

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ID Code: 71934
Item Type: Journal Article
Refereed: Yes
Keywords: ab initio calculations, carbonyl complexes, germanium, interstellar, molecules, mass spectrometry, silicon, gaussian-basis sets, correlated molecular calculations, electron-spin-resonance, orbital methods, monoxide, atoms, chemistry, spectra
DOI: 10.1002/(sici)1521-3765(20000403)6:7<1236::aid-chem1236>3.3.co;2-v
ISSN: 1521-3765 (online) 0947-6539 (print)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright © 2000 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany
Deposited On: 26 May 2014 00:07
Last Modified: 18 Jan 2016 04:48

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