Theoretical study of the mechanism of cycloaddition reaction between dichloromethylene silylene and formaldehyde

Lü, Xin; Yu, Haizhu; Xu, Yuehua; Xiang, Pingping; Che, Xin

doi:10.1080/00268970701496532

Cited by 12 publications

(1 citation statement)

References 16 publications

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“…The energy of H 2 C=Si: Is 84 kcal/mol lower than that of silaacetylide, H 2 C=Si: Is the lowest energy isomer [3]. We have performed some studies on the cycloaddition reaction of unsaturated silylenes preliminarily [4,5], but these studies are limited to the cycloaddition reaction of methylene silylene and its derivatives [R 1 , R 2 C=Si: (R 1 , R 2 =H, Me, F, Cl, Br, Ph, Ar . .…”

Section: Introductionmentioning

confidence: 99%

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Lü

Ming

Han

2014

Main Group Chemistry

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The mechanism of the cycloaddition reaction between singlet state Cl 2 Ge=Si: And acetone has been investigated with density functional theory (DFT). From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The presented rule of the reaction is that the [2+2] cycloaddition effect of the two p-bonds in Cl 2 Ge=Si: And acetone leads to the formation of two four-membered Ge-heterocyclic ring silylenes (1. Ge and O in the opposite orientation; 2. Ge and O in the syn-position). Because of the 3p unoccupied orbital of the Si: Atom in two four-membered Ge-heterocyclic ring silylenes and the π orbital of acetone forming a π −→ p donor-acceptor bond, the two four-membered Ge-heterocyclic ring silylenes further combines with acetone to form an intermediate, respectively. Because the Si atom in two intermediates happens sp 3 hybridization after transition state, then, two intermediates isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state, respectively.

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Section: Introductionmentioning

confidence: 99%

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Lü

Ming

Han

2014

Main Group Chemistry

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Theoretical Study of the Mechanism of Cycloaddition Reaction between Silylene Silylene (H₂SiSi:) and Acetone

Wang

Shi

et al. 2011

Chin. J. Chem.

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The mechanism of the cycloaddition reaction between singlet silylene silylene (H2SiSi:) and acetone has been investigated with the CCSD (T)//MP2/6‐31G∗︁ method. According to the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction channels. The present rule of this reaction is that the [2+2] cycloaddition reaction of the two π‐bonds in silylene silylene (H2SiSi:) and acetone leads to the formation of a four‐membered ring silylene (E3). Because of the unsaturated property of Si: atom in E3, it further reacts with acetone to form a silicic bis‐heterocyclic compound (P7). Simultaneously, the ring strain of the four‐membered ring silylene (E3) makes it isomerize to a twisted four‐membered ring product (P4).

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Ab initio Study of Mechanism of Cycloaddition Reaction between Germylene Silylene (H₂GeSi:) and Acetone

Lü

Han

et al. 2011

Chin. J. Chem.

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The mechanism of the cycloaddition reaction between singlet germylene silylene (H2GeSi:) and acetone has been investigated with CCSD(T)/6‐31G*//MP2/6‐31G* method. From the potential energy profile, we could predict that the reaction has two competitive dominant reaction channels. The present rule of this reaction is that the [2+2] cycloaddition reaction of the two (‐bonds in germylene silylene and acetone generates a four‐membered ring silylene with Ge. Because of the unsaturated property of Si atom in the four‐membered ring silylene with Ge, it could further react with acetone, resulting in the generation of a bis‐heterocyclic compound with Si and Ge. Simultaneously, the ring strain of the four‐membered ring silylene with Ge makes it isomerize to a twisted four‐membered ring product.

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Theoretical study of the mechanism of cycloaddition reaction between dichloromethylene silylene and formaldehyde

Cited by 12 publications

References 16 publications

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Theoretical Study of the Mechanism of Cycloaddition Reaction between Silylene Silylene (H₂SiSi:) and Acetone

Ab initio Study of Mechanism of Cycloaddition Reaction between Germylene Silylene (H₂GeSi:) and Acetone

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Theoretical study of the mechanism of cycloaddition reaction between dichloromethylene silylene and formaldehyde

Cited by 12 publications

References 16 publications

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Density functional theory study of mechanism of forming a spiro-Si-heterocyclic ring compound involving Ge from Cl2Ge=Si: And acetone

Theoretical Study of the Mechanism of Cycloaddition Reaction between Silylene Silylene (H2SiSi:) and Acetone

Ab initio Study of Mechanism of Cycloaddition Reaction between Germylene Silylene (H2GeSi:) and Acetone

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Theoretical Study of the Mechanism of Cycloaddition Reaction between Silylene Silylene (H₂SiSi:) and Acetone

Ab initio Study of Mechanism of Cycloaddition Reaction between Germylene Silylene (H₂GeSi:) and Acetone