Toward unsaturated stannylenes Y<sub>2</sub>ZSn: and related compounds with triplet electronic ground states

Bundhun, Ashwini; Momeni, Mohammad R.; Shakib, Farnaz A.; Ramasami, Ponnadurai; Gaspar, Peter P.; Schaefer, Henry F.

doi:10.1039/c6ra00492j

Cited by 5 publications

(5 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…So, the ground state of Me 2 Si=Sn: is a singlet state. On this issue, Bundhun et al 15 also made relevant reports. Theoretical research shows that the cycloaddition reaction between singlet state Me 2 Si=Sn: and ethene has the following two possible pathways.…”

Section: Resultsmentioning

confidence: 98%

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene

Tan

Lü

2019

Progress in Reaction Kinetics and Mechanism

View full text Add to dashboard Cite

X2Si=Sn: (X = H, Me, F, Cl, Br, Ph, Ar, etc.) are a new chemical species. The cycloaddition reactions of X2Si=Sn: are a new field of stannylene chemistry. The mechanism of the cycloaddition reaction between singlet state Me2Si=Sn: and ethene has been investigated for the first time here using second-order Møller-Plesset perturbation theory together with the 6-311++G** basis set for C, H and Si atoms and the LanL2dz basis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction process presented is that the 5p unoccupied orbital of Sn in Me2Si=Sn: and the π orbital of ethene form a π → p donor–acceptor bond resulting in the formation of an intermediate. The instability of this intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of the Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethene form a π → p donor–acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in this intermediate assumes sp3 hybridization after the transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. This result indicates the modes of cycloaddition reactions between X2Si=Sn: and symmetric π-bonded compounds, i.e. this study opens up a new field for stannylene chemistry.

show abstract

Section: Resultsmentioning

confidence: 98%

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene

Tan

Lü

2019

Progress in Reaction Kinetics and Mechanism

View full text Add to dashboard Cite

show abstract

“…For hydrogen, a set of p polarization functions α d (H) = 0.75 was added to the Huzinaga–Dunning DZ set . For the first-row transition metals, Wachters’ basis sets were used in our loosely compressed DZP basis set supplemented by two sets of p functions and one set of d functions and then contracted following Hood et al and designated (14s11p6d/10s8p3d). , Each hydrogen atom basis set was augmented with one diffuse s-function …”

Section: Theoretical Methodsmentioning

confidence: 99%

“…19,20 Each hydrogen atom basis set was augmented with one diffuse s-function. 21 We fully optimized the geometries of all structures at the OPBE/ DZP level of theory. The fine grid (75 radial shells, 302 angular points) was the default value for numerical integration, and the tight (10 −8 hartree) designation was the default value for the self-consistent field (SCF) energy convergence.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Tetrahedral Cyclopentadienylmetal Carbonyl Clusters of Manganese and Chromium: A Theoretical Study

Liu

Zhang

et al. 2021

Inorg. Chem.

View full text Add to dashboard Cite

Tetranuclear Cp4M4(CO)4 clusters have been synthesized for iron and vanadium but not for the intermediate first-row transition metals manganese and chromium. All of the low-energy structures of these “missing” Cp4M4(CO)4 (M = Mn, Cr) species are shown by density functional theory to consist of a central M4 tetrahedron with each of the four faces capped by a μ3-CO group. The individual low-energy structures differ in their spin states and in their formal metal–metal bond orders along the six edges of their central M4 tetrahedra. The two low-energy Cp4Mn4(μ3-CO)4 structures are a triplet structure with all Mn–Mn single bonds and a singlet structure with one MnMn triple bond and five Mn–Mn single bonds along the six tetrahedral edges. Related low-energy Cp4Cr4(μ3-CO)4 structures include a quintet structure with all Cr–Cr single bonds and a singlet structure with two CrCr triple bonds and four Cr–Cr single bonds. However, the potential energy surface of the Cp4Cr4(CO)4 system is complicated by three other structures of comparable energies including two triplet structures and one quintet structure with various combinations of single, double, and triple chromium–chromium bonds in the central Cr4 tetrahedron.

show abstract

“…Their cycloaddition reaction has been studied [7][8][9][10][11], With the progress of these studies, research on unsaturated stannylene has been mentioned on the agenda. At present, Bundhun et al have conducted very good research on unsaturated stannylene [12]. But there has been no published reports about cycloaddition reactions of unsaturated stannylene till now.…”

Section: Introductionmentioning

confidence: 99%

Features of Mechanism of Cycloaddition Reaction between H2Sn=Sn: and Ethylene

Tan

Lü

2019

Russ. J. Phys. Chem.

View full text Add to dashboard Cite

X 2 Sn=Sn: (X = H, Me, F, Cl, Br, Ph, Ar, …) are new species of chemistry. The cycloaddition reaction of X 2 Sn=Sn: are new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X 2 Sn=Sn: and the symmetric π-bonded compounds, the cycloaddition reactions of H 2 Sn=Sn: and ethylene were selected as model reactions in this paper. The mechanism of cycloaddition reaction between singlet H 2 Sn=Sn: and ethylene has been first investigated with the MP2/GENECP (C, H in 6-311++G**; Sn in LanL2dz) method in this paper. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule presented is that the two reactants firstly form a four-membered Sn-heterocyclic ring stannylene through the [2 + 2] cycloaddition reaction. Because of the 5p unoccupied orbital of Sn: atom in the four-membered Sn-heterocyclic ring stannylene and the π orbital of ethylene forming a π → p donor-acceptor bond, the four-membered Sn-heterocyclic ring stannylene further combines with ethylene to form an intermediate. Because the Sn: atom in intermediate happens sp 3 hybridization after transition state, then, intermediate isomerizes to a spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X 2 Sn=Sn: and the symmetric π-bonded compounds. The study opens up a new research field for stannylene chemistry.

show abstract

Toward unsaturated stannylenes Y₂ZSn: and related compounds with triplet electronic ground states

Abstract: Distribution of electrons between the Y2Z: moiety and the triplet Sn atom in Y2ZSn: and representations of singlet and triplet Y2ZSn: and Y2Z: electronic configurations.

Cited by 5 publications

References 26 publications

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene

Tetrahedral Cyclopentadienylmetal Carbonyl Clusters of Manganese and Chromium: A Theoretical Study

Features of Mechanism of Cycloaddition Reaction between H2Sn=Sn: and Ethylene

Contact Info

Product

Resources

About

Toward unsaturated stannylenes Y2ZSn: and related compounds with triplet electronic ground states

Abstract: Distribution of electrons between the Y2Z: moiety and the triplet Sn atom in Y2ZSn: and representations of singlet and triplet Y2ZSn: and Y2Z: electronic configurations.

Cited by 5 publications

References 26 publications

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene

Tetrahedral Cyclopentadienylmetal Carbonyl Clusters of Manganese and Chromium: A Theoretical Study

Features of Mechanism of Cycloaddition Reaction between H2Sn=Sn: and Ethylene

Contact Info

Product

Resources

About

Toward unsaturated stannylenes Y₂ZSn: and related compounds with triplet electronic ground states

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me₂Si=Sn: and ethene