Computational study on 1, 3‐disilacyclobutane‐1, 3‐diylidene disilylenes: A synthetic strategy for cis‐bent disilenes†. (13th June 2017)

• Record Type: Journal Article
• Authors: Fujita, Yoshiki; Abe, Manabu
• Other Names: Ihmels Heiko guestEditor.; Linker Torsten guestEditor.; Trofimov Aleksei guestEditor.
• Is Part Of: Journal of physical organic chemistry. Volume 30:Number 9(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2017-06-13
• Subjects: coupled‐cluster calculations -- density functional theory -- disilenes -- spin multiplicity; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3724
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract : Coupled‐cluster calculations were performed for 1, 3‐disilacyclobutane‐1, 3‐diylidene disilylenes at the CCSD(T)//CCSD/cc‐pVDZ level of theory to investigate the ground‐state spin multiplicity and structures of these unique molecules in detail. The cis ‐bent disilene with an R2 Si═SiR2 double‐bonding structure was found to be the most energetically stable structure for the 2, 2, 4, 4‐tetrafluoro‐substituted compound. In contrast, the singlet disilylene structures (R2 Si:) with a 4‐membered ring geometry were calculated to be more energetically stable than the disilene structures for 1, 3‐disilacyclobutane‐1, 3‐diylidene disilylenes with electron‐donating substituents such as H and SiH3 . Thus, the perfluoro‐substituted disilylene was found to be a candidate for the synthesis of cis ‐bent disilenes. Abstract : The cis ‐bent disilene with an R2 Si═SiR2 double‐bonding structure was found to be the most energetically stable structure for the 2, 2, 4, 4‐tetrafluoro‐substituted compound. In contrast, the singlet disilylene structures (R2 Si:) with a 4‐membered ring geometry were calculated to be more energetically stable than the disilene structures for 1, 3‐disilacyclobutane‐1, 3‐diylidene disilylenes with electron‐donating substituents such as H and SiH3 .