Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives

Mitzel NW, Schmidbaur H, Rankin DWH, Smart BA, Hofmann M, Schleyer PV (1997)
INORGANIC CHEMISTRY 36(20): 4360-4368.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
An optimized synthetic procedure for alpha,omega-bis (bromosilyl)alkanes, BrH2Si(CH2)(w)SiH2Br (with n = 2 and 3), is proposed. I,2-Bis(bromosilyl)ethane reacts with ammonia to give 1,4-bis(1-aza-2,5-disilacyclopentane-1-yl)-1,4-disilabutane, traces of 1,6-diaza-2,5,7,10,11,14-hexasilabicyclo[4.4.4]tetradecane and nonvolatile products. The primary reaction products undergo slow redistribution reactions whereby (1-aza-2,5-disilacyclopentane-1-yl)-1,4-disilabutane is formed as the major product. Reactions of alpha,omega-bis(bromosilyl)alkanes, BrH2Si(CH2)(n)SiH2Br (with n = 2 and 3), with isopropylamine afford the heterocycles 1-isopropyl-1-aza-2,5-disilacyclopentane and 1-isopropyl-1-aza-2,6-disilacyclohexane, whereas the analogous reaction with bis(bromosilyl)methane gives 1,5-diisopropyl-1,5-diaza-2,4,6,8-tetrasilacyclooctane rather than a four-membered ring compound. All compounds have been characterized by elemental analysis, mass spectrometry, and IR and NMR spectroscopy [H-1, C-13, N-15 and Si-29 including the measurement of (1)J((SiN)-Si-29-N-15) coupling constants]. The molecular structure of 1-isopropyl-1-aza-2,5-disilacyclopentane, determined by analysis of gas-phase electron-diffraction data augmented by restraints derived from ab initio calculations, is compared with the molecular structure of the isoelectronic 1-(dimethylamino)-1-aza-2,5-disilacyclopentane . The latter also was determined by gas-phase electron-diffraction (Supported by nb initio calculations) and by low-temperature crystallography. The presence of a beta-donor Si...N interaction in the tatter compound, leading to a narrow Si-N-N angle, is apparent from a significant distortion of the molecular structure as compared with the isoelectronic reference compound.
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INORGANIC CHEMISTRY
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36
Zeitschriftennummer
20
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4360-4368
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Mitzel NW, Schmidbaur H, Rankin DWH, Smart BA, Hofmann M, Schleyer PV. Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives. INORGANIC CHEMISTRY. 1997;36(20):4360-4368.
Mitzel, N. W., Schmidbaur, H., Rankin, D. W. H., Smart, B. A., Hofmann, M., & Schleyer, P. V. (1997). Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives. INORGANIC CHEMISTRY, 36(20), 4360-4368. doi:10.1021/ic9703179
Mitzel, N. W., Schmidbaur, H., Rankin, D. W. H., Smart, B. A., Hofmann, M., and Schleyer, P. V. (1997). Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives. INORGANIC CHEMISTRY 36, 4360-4368.
Mitzel, N.W., et al., 1997. Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives. INORGANIC CHEMISTRY, 36(20), p 4360-4368.
N.W. Mitzel, et al., “Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives”, INORGANIC CHEMISTRY, vol. 36, 1997, pp. 4360-4368.
Mitzel, N.W., Schmidbaur, H., Rankin, D.W.H., Smart, B.A., Hofmann, M., Schleyer, P.V.: Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives. INORGANIC CHEMISTRY. 36, 4360-4368 (1997).
Mitzel, Norbert W., Schmidbaur, H, Rankin, DWH, Smart, BA, Hofmann, M, and Schleyer, PV. “Synthesis of volatile cyclic silylamines and the molecular structures of two 1-aza-2,5-disilacyclopentane derivatives”. INORGANIC CHEMISTRY 36.20 (1997): 4360-4368.

7 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

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Hayes SA, Berger RJ, Neumann B, Mitzel NW, Bader J, Hoge B., Dalton Trans 39(24), 2010
PMID: 20379589
Syntheses and structures of (N',N'-dimethylhydrazido)silanes.
Gronde I, Neumann B, Willner A, Pape T, Mitzel NW., Dalton Trans (27), 2009
PMID: 19565082
Highly asymmetric coordination of trimethylsilyl groups to tetrazole and triazole rings: an experimental and computational study in gaseous and crystalline phases.
Wann DA, Gronde I, Foerster T, Hayes SA, Masters SL, Robertson HE, Mitzel NW, Rankin DW., Dalton Trans (29), 2008
PMID: 18629403
Steric and electronic effects on the conformations of n-butane derivatives with trichlorosilyl, silyl and trichloromethyl groups.
McLachlan LJ, Hinchley SL, Robertson HE, Rankin DW, Mitzel NW., Spectrochim Acta A Mol Biomol Spectrosc 61(7), 2005
PMID: 15820874

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