title: Ab initio study of mechanism of forming a spiro-heterocyclic ring compound with Si and Ge between dimethylsilylene germylidene (Me(2)Si = Ge:) and acetone.
abstract: The mechanism of the cycloaddition reaction between singlet state dimethylsilylene germylidene (Me(2)Si = Ge:) and acetone has been investigated with CCSD(T)//B3LYP/6-31G* method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rules presented are that the two reactants first form a Si-heterocyclic four-membered ring germylene through the [2 + 2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic four-membered ring germylene and the π orbital of acetone forming a π→p donor-acceptor bond, the Si-heterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate happens sp(3) hybridization after transition state, then, the intermediate isomerizes to a spiro-heterocyclic ring compound with Si and Ge via a transition state.
authors.affiliation: School of Chemistry and Chemical Engineering, University of Jinan, Jinan, Shandong, 250022, People's Republic of China. lxh@ujn.edu.cn
authors.forename: Xiuhui
authors.initials: X
authors.lastname: Lu
authors.forename: Zhenxia
authors.initials: Z
authors.lastname: Lian
authors.forename: Yongqing
authors.initials: Y
authors.lastname: Li
authors.forename: Zhina
authors.initials: Z
authors.lastname: Wang
mesh_terms: D000096:Acetone / Q000737:chemistry*; D061565:Cycloaddition Reaction; D005857:Germanium / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D012825:Silicon / Q000737:chemistry*; D017655:Silicon Compounds / Q000737:chemistry; D013141:Spiro Compounds / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D006571:Heterocyclic Compounds; D017655:Silicon Compounds; D013141:Spiro Compounds; D005857:Germanium; D000096:Acetone; D012825:Silicon