A theoretical survey of singly bonded silicon compounds.  Comparison of the structures and bond energies of silyl and methyl derivatives

Luke, Brian T.; Pople, J. A.; Krogh-Jespersen, M.-B.; Apeloig, Yitzhak; Chandrasekhar, Jayaraman; Schleyer, Paul v. R.

doi:10.1021/ja00262a013

Cited by 173 publications

(56 citation statements)

References 22 publications

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“…In investigations on synthetic applications of thermally generated alkoxy- [4] and aminosubstituted [4,5] silylenes, which are less n--stabilized (about 15 to 23 kcal/mol [ 6 ] ) , we found no prinDedicated to Prof. Dr. K. Ruhlmann (Dresden) on the occa-"To whom correspondence should be addressed. Cycloadditions of methoxymethylsilylene to oxaand azadienes are, in many respects, closely related to the diene reactions.…”

Section: Introductionmentioning

confidence: 83%

Methoxymethylsilylene: (1 + 6)‐ and (1 + 4)‐cycloadditions to heterotrienes

Heinicke¹,

Gehrhus²

1995

Heteroatom Chemistry

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Section: Introductionmentioning

confidence: 83%

Methoxymethylsilylene: (1 + 6)‐ and (1 + 4)‐cycloadditions to heterotrienes

Heinicke¹,

Gehrhus²

1995

Heteroatom Chemistry

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“…These are considerably red shifted compared with the H or C terminated polyynes (20,31). r-Interactions may arise from either (n-d)r or (p-d)r (32) (or (n-u*)r or (p-u*)r) interaction^.^ These would be anticipated to occur through u*-orbitals in the case of silicon; d orbitals are apparently not very important in the interaction with first-row elements (32,33). There is expected to be an increased propensity for d orbital involvement with the lower Group 14 elements.…”

Section: Discussionmentioning

confidence: 99%

Tetrakis[(trimethylsilyl)ethynyl] Group 14 metal derivatives: an examination of the electronic interaction between two Group 14 metals connected by an acetylene wire

Dallaire¹,

Brook²,

Bain³

et al. 1993

Can. J. Chem.

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The tetrakis(trimethylsilyl)ethynyl derivatives of Si, Ge, Sn, and Pb were prepared and examined spectroscopically. NMR and Mössbauer spectroscopy and X-ray crystal structure data clearly demonstrate an electronic interaction in the ground state between the distal SiMe3 groups and the central metal atom, leading to a strong shielding of the central metal atom; the respective nmr signals of the central metal are among the most shielded examples reported for a tetrahedral Group 14 metal centre with four carbon ligands. The nature of these electronic interactions is discussed.

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“…In this work, we will be using the bond distance between atoms in well-known compounds as a standard to infer the single, double, or triple character of the bonds. In the case of bonds between two silicon atoms, we have disilane as a reference for a standard single bond (2.34 Å) 41 , and Si 2 for a double (2.25 Å) 42 . Between silicon and nitrogen, H 3 Si-NH 2 illustrates a typical single bond (1.72 Å) 43,44 and H 2 Si=NH is a model for a double bond (1.58 Å) 45 ; finally, between two nitrogens, N 2 is a standard for a triple bond (1.098 Å) 46 , diazene HN=NH for a double bond (1.252 Å) [47][48][49] , and H 2 N-NH 2 for a single bond (1.414 Å) 50 .…”

Section: Structures and Energetics Of Si 3 N 2 Speciesmentioning

confidence: 99%

Structures and energetics of Si3N2 clusters

Ueno

Ornellas

2001

J. Braz. Chem. Soc.

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Aglomerados mistos de silício e nitrogênio com fórmula Si 3 N 2 foram investigados teoricamente com os métodos SCF e MP2. Dos onze pontos estacionários encontrados abaixo de 80 kcal/mol, oito correspondem a mínimos locais (ML); desses, cinco são estados singletos. Quanto aos tripletos, três ML e um estado de transição (ET) foram caracterizados. O mínimo global corresponde a uma estrutura angular com ligações alternadas silício-nitrogênio, que contrasta com as estruturas lineares de outros aglomerados menores de Si/N. Uma estrutura bipiramidal mais alta em energia 41.0 kcal/mol pode ser vista como um padrão natural para um crescimento tridimensional. Em geral, estruturas com mais ligações SiN são preferidas energeticamente em relação àquelas em que as ligações SiSi predominam. Tentativas para se localizar ET que se correlacionam com os canais de dissociação mais baixos não tiveram sucesso devido à complexa e computacionalmente difícil busca. Apesar disso, garante-se a estabilidade termodinâmica das estruturas I, III, IV e V, sendo a energia do canal mais baixo um limite inferior. A energia de atomização da estrutura do mínimo global é de 420.6 kcal/mol (MP2).Mixed clusters of silicon and nitrogen with formula Si 3 N 2 have been investigated at both SCF and MP2 levels of theory. Of eleven stationary points found below 80 kcal/mol, eight correspond to local minima (LM); of these, five are singlet states. Of the triplets, three LM and one transition state (TS) were characterized. The global minimum corresponds to an angular structure with alternating siliconnitrogen bonds, in contrast with linear ones for other smaller Si/N clusters. A bipyramidal structure 41.0 kcal/mol high in energy can be seen as a natural pattern for tridimensional growing. In general, structures with more SiN bonds are energetically preferred to those in which the SiSi bonds predominate. Attempts to locate TS correlating with the lowest dissociation channels have been unsuccessful due the complex and computationally demanding search. Despite this fact, the thermodynamic stability for structures I, III, IV, and V is guaranteed, being the energy of the lowest channel a lower bound. The atomization energy for the global minimum structure amounts to 420.6 kcal/mol (MP2).

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A theoretical survey of singly bonded silicon compounds. Comparison of the structures and bond energies of silyl and methyl derivatives

Cited by 173 publications

References 22 publications

Methoxymethylsilylene: (1 + 6)‐ and (1 + 4)‐cycloadditions to heterotrienes

Methoxymethylsilylene: (1 + 6)‐ and (1 + 4)‐cycloadditions to heterotrienes

Tetrakis[(trimethylsilyl)ethynyl] Group 14 metal derivatives: an examination of the electronic interaction between two Group 14 metals connected by an acetylene wire

Structures and energetics of Si3N2 clusters

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