Molecular structure and bonding of a silacyclopropane, dimethyldispiro[bicyclo[4.1.0]heptane-7,2'-silacyclopropane-3',7''-bicyclo[4.1.0]heptane]

Delker, Gerald L.; Wang, Yu; Stucky, Galen D.; Lambert, Robert L.; Haas, Carol K.; Seyferth, Dietmar

doi:10.1021/ja00423a024

Cited by 64 publications

(17 citation statements)

References 5 publications

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“…An interesting aspect of the structure 179 is 705 Brought to you by | Purdue University Libraries Authenticated Download Date | 6/15/15 8:30 PM the deformation of the naphthalene fragments, the naphthalene carbon atoms bonded to silicon being "pulled" out of the plane in the direction of the bridging Me 2 Si group. To a lesser extent, this is also true for C (2) , but the other carbon atoms (C (3) , C (4) , C (5) , C (6) , C (9) , C (10) ) all remain in the original plane. The torsion C (1) C(9)C( 1 o)C (5) angle of 11.6° is a good quantitative indication of the distortion of the naphthalene moiety.…”

Section: Silacyclooctanesmentioning

confidence: 90%

“…As a rule, the two intramolecular Si-X (1) and Si-X (2) distances are not equivalent and differ by 0.75-0.82 Ä, only in the selenium derivative 185 with R=Me the Si Se distances differ by a lesser extent (4.322 and 4.228 Ä), the molecule having an approximate twofold symmetry axis. The shorter intramolecular Si-X {2) distance for the selenium (R=Ph) and both sulfur (R=Me, Ph) compounds is less than the sum of van der Waals radii, thus confirming the transannular interaction between silicon and sulfur or selenium.…”

Section: Compounds With Larger Ringsmentioning

confidence: 95%

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Molecular Structure of Sila-Heterocycles

Lukevics¹,

Pudova²

1998

Main Group Metal Chemistry

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The present review provides a comprehensive survey on the molecular structure of silaheterocyclic compounds (silacyclopropanes, silacyclobutanes, silacyclopentanes, silacyclohexanes and derivatives with larger rings, as well as compounds with fused and unsaturated heterocycles). In a lot of cases the heterocycles include also heteroatoms other than silicon, however, all silaheterocycles under consideration contain only Si-C bonds. INTRODUCTIONThe results of the structural investigations of the organosilicon heterocycles were reviewed in 1989 [1], However, sila-heterocycles have been the subject of extensive studies over the last 10 years. Much attention has been focused on the synthesis and structural characterization both derivatives with small rings and the macrocyclic compounds. There has been also a considerable interest in the cyclic π-electronic systems containing the silicon atom. Much of this interest concerns the possibility of aromatic character for the silole anions and dianions. Recently the first neutral silaaromatic compound -2-silanaphthalene was successfully isolated and structurally characterized. Our review is an attempt to summarize and systematize the numerous papers scattered in literature on this subject.

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Section: Silacyclooctanesmentioning

confidence: 90%

Section: Compounds With Larger Ringsmentioning

confidence: 95%

Molecular Structure of Sila-Heterocycles

Lukevics¹,

Pudova²

1998

Main Group Metal Chemistry

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“…Particularly in the case of phosphonium sila-ylide 1 c, which has a weaker nucleophilic diphenylphosphine ligand, the reaction results in the formation of a perfectly stable silirane 2 c. Indeed, the fact that Si À P bond in 2 c (3.323 ) is slightly longer than that in 2 a suggests a weaker P À Si interaction (Figure 1 b). [18] The calculations for the formation of 2 c reveal a more exothermic reaction (DG = À6.63 kcal mol À1 ). These results are consistent with the previously reported ligand-dependent thermal stability of the neutral pentacoordinated silicon species, in their ligand coupling reactions.…”

mentioning

confidence: 92%

“…[18] The molecule shows a strongly distorted trigonal-bipyramidal (TBP) geometry around the pentacoordinate silicon center with the phosphorus atom and one methylene group at the apical positions (P-Si-C5 = 147.08). The sum of the equatorial bond angles around the silicon atom (358.58) is close to the ideal value for the TBP geometry.…”

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confidence: 99%

Reversible Binding of Ethylene to Silylene–Phosphine Complexes at Room Temperature

et al. 2011

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“…With respect to cyclopropane, introduction of a heteroatom into the small ring decreases the distal C-C ring bond length (Bak & Skaarup, 1971;Ito & Sakurai, 1973;Delker, Wang, Stucky, Lambert, Haas & Seyferth, 1976;Allen, 1982), while the n-acceptor substituents shorten the distal bond and lengthen the vicinal (Lauher & Ibers, 1975;Deakyne, Allen & Laurie, 1977;Allen, 1980Allen, , 1982: the result may be approximated as a summation of asymmetries induced by each individual effect. In the title compound the C(3)-C(4) bond is shorter than the normal Cspr-Csp3 bond but is longer than the corresponding bond in pure unsubstituted aziridine [mean value 1.484 (3)~ in Allen, 1982]; the N(3)-C(4) bond is longer than the N(3)-C(3) bond in accord with the substituent effect.…”

mentioning

confidence: 99%