title: An ab initio and density functional theory study of the structure and bonding of sulfur ylides.
abstract: Sulfur ylides are useful synthetic intermediates that are formed from the interaction between singlet carbenes and sulfur-containing molecules. Partial double-bond character frequently has been proposed as a key contributor to the stability of sulfur ylides. Calculations at the B3LYP, MP2, and CCSD(T) levels of theory employing various basis sets have been performed on the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) in order to investigate the structure and bonding of these systems. The following general properties of sulfur ylides were observed from the computational studies: C-S bond distances that are close in length to that of a typical C-S double bond, high charge transfer from the sulfide to the carbene, and large torsional rotation barriers. Analysis of the sulfur ylide charge distribution indicates that the unusually short C-S bond distance can be attributed in part to the electrostatic attraction between highly oppositely charged carbon and sulfur atoms. Furthermore, n --> sigma* stabilization arising from donation of electron density from the carbon lone pair orbital into S-H or S-C antibonding orbitals leads to larger than expected torsional barriers. Finally, natural resonance theory analysis indicates that the bond order of the sulfur ylides H(2)S-CH(2) and (CH(3))(2)S-CH(2) is 1.4-1.5, intermediate between a single and double bond.
authors: Department of Chemistry, Illinois State University, Normal, Illinois 61790-4160, USA. standard@ilstu.edu
authors: Jean M
authors: JM
authors: Standard
authors: Beth A
authors: BA
authors: Copack
authors: Tami K
authors: TK
authors: Johnson
authors: David E
authors: DE
authors: Przybyla
authors: Shelley R
authors: SR
authors: Graham
authors: Rebecca J
authors: RJ
authors: Steidl