The shapes and other properties of non-transition element complexes. 3. AB5

Gimarc, Benjamin M.

doi:10.1021/ja00476a014

Cited by 18 publications

(10 citation statements)

References 29 publications

(29 reference statements)

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“…These have eight valence electrons and so may be recognized as a class of species ignored in the earlier qualitative molecular orbital treatment of non-transition metal, but otherwise general AB 5 species even though most species of this type have 10 or 12 valence electrons (Gimarc, 1978). Nonetheless, we will use the correlation diagram and other analyses found in this study.…”

Section: Concluding Remarks 41 Chemical Considerationsmentioning

confidence: 99%

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Vegas

Notario

Chamorro

et al. 2013

Acta Crystallogr Sect B

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A topological analysis of the electron localization function (ELF) of a molecule of hexamethyldisiloxane, (H 3 C) 3 -Si-OSi-(CH 3 ) 3 , has been carried out, drawing a consistent picture of Si-O-Si bonding both in the linear and angular geometries. The ELF analysis confirms the idea that the O atom, in the linear geometry of (H 3 C) 3 -Si-O-Si-(CH 3 ) 3 , is isolobal with the isoelectronic -CH þ 3 -and -BH 3 -groups, the bonding in the Si-O-Si group being described as a two-electron, three-center (2e, 3c) bond. At the same time, the three oxygen lone pairs mirror the three C-H and B-H bonds, respectively. On the contrary, in the angular geometry the same O atoms form two Si-O bonds and its lone pairs mimic the geometry of the -CH 2 -group. In this model the O atoms would play the same role as the formally present O 2À anions in the 'so-called' ionic solids, such as in the skeletons of aluminate and silicate polyanions, thereby connecting molecular and solid-state chemistry as formulated by the 'fragment formalism' or the 'molecular unit-cell approach'. This unifying concept as well as the calculations we have carried out fully agree and also give support to earlier ideas developed by Bragg and Bent, among other authors. Bonding in the series of compounds P 4 , P 4 O 6 , P 4 O 10 , N 4 (CH 2 ) 6 (hexamethylenetetramine) and (CH) 4 (CH 2 ) 6 (adamantane) is discussed in the context of the isolobal model.

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Section: Concluding Remarks 41 Chemical Considerationsmentioning

confidence: 99%

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Vegas

Notario

Chamorro

et al. 2013

Acta Crystallogr Sect B

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“…Pentacoordinate silicon has been the subject of theoretical studies that focused mainly on the type of bonding and the reason for the stability of SiH 5 - as compared to that of CH 5 - . − Also axial versus equatorial substitution and intramolecular ligand interchange have been addressed . However, reactivity studies have been limited to possible H 2 elimination and the mechanism of nucleophilic halogen substitution at tetracoordinate silicon .…”

Section: Introductionmentioning

confidence: 99%

Electronic Structure and Stability of Pentaorganosilicates

et al. 2006

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The exceptional stability of recently reported pentaorganosilicates is investigated by bond energy analyses. Experimental coupling constants are used to probe their electronic structure, entailing bonds with mixed ionic-covalent character. Our analyses reconfirm that the axial bonds are more prone to heterolytic cleavage than are the equatorial bonds. Aryl substituents provide substantial electronic stabilization by charge delocalization, but cause steric crowding due to ortho-hydrogen repulsion. In contrast, silicates with two ax,eq biaryl groups are not congested. The remaining substituent is confined to an equatorial site, where it is insensitive to elimination. These concepts adequately explain the experimentally observed stability trends and are valuable for designing other stable pentaorganosilicates.

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“…We now return to [(H 3 C) 3 -Si-CH 3 -Si-(CH 3 ) 3 ] þ and [(H 3 C) 3 -Si-BH 3 -Si-(CH 3 ) 3 ] with linear Si-X-Si (X = C and B) substructures and put these 'exotic' species into more classical chemical context. These have eight valence electrons and so may be recognized as a class of species ignored in the earlier qualitative molecular orbital treatment of non-transition metal, but otherwise general AB 5 species even though most species of this type have 10 or 12 valence electrons (Gimarc, 1978). Nonetheless, we will use the correlation diagram and other analyses found in this study.…”

Section: Concluding Remarks 41 Chemical Considerationsmentioning

confidence: 99%

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Vegas

Notario

Chamorro

et al. 2013

Acta Crystallogr Sect B

View full text Add to dashboard Cite

A topological analysis of the electron localization function (ELF) of a molecule of hexamethyldisiloxane, (H3C)3-Si-O-Si-(CH3)3, has been carried out, drawing a consistent picture of Si-O-Si bonding both in the linear and angular geometries. The ELF analysis confirms the idea that the O atom, in the linear geometry of (H3C)3-Si-O-Si-(CH3)3, is isolobal with the isoelectronic -CH3(+)- and -BH3- groups, the bonding in the Si-O-Si group being described as a two-electron, three-center (2e, 3c) bond. At the same time, the three oxygen lone pairs mirror the three C-H and B-H bonds, respectively. On the contrary, in the angular geometry the same O atoms form two Si-O bonds and its lone pairs mimic the geometry of the -CH2- group. In this model the O atoms would play the same role as the formally present O(2-) anions in the `so-called' ionic solids, such as in the skeletons of aluminate and silicate polyanions, thereby connecting molecular and solid-state chemistry as formulated by the `fragment formalism' or the `molecular unit-cell approach'. This unifying concept as well as the calculations we have carried out fully agree and also give support to earlier ideas developed by Bragg and Bent, among other authors. Bonding in the series of compounds P4, P4O6, P4O10, N4(CH2)6 (hexamethylenetetramine) and (CH)4(CH2)6 (adamantane) is discussed in the context of the isolobal model.

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The shapes and other properties of non-transition element complexes. 3. AB5

Cited by 18 publications

References 29 publications

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Electronic Structure and Stability of Pentaorganosilicates

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

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The shapes and other properties of non-transition element complexes. 3. AB5

Cited by 18 publications

References 29 publications

Isoelectronic and isolobal O, CH2, CH3+and BH3as electron pairs; similarities between molecular and solid-state chemistry

Isoelectronic and isolobal O, CH2, CH3+and BH3as electron pairs; similarities between molecular and solid-state chemistry

Electronic Structure and Stability of Pentaorganosilicates

Isoelectronic and isolobal O, CH2, CH3+and BH3as electron pairs; similarities between molecular and solid-state chemistry

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Product

Resources

About

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry

Isoelectronic and isolobal O, CH₂, CH₃⁺and BH₃as electron pairs; similarities between molecular and solid-state chemistry