The gas-phase equilibrium structures of Si 8O 12(OSiMe 3) 8 and Si 8O 12(CHCH 2) 8

D.A. Wann; C.N. Dickson; P.D. Lickiss; H.E. Robertson; D.W.H. Rankin

doi:10.1021/ic102457w

The gas-phase equilibrium structures of Si 8O 12(OSiMe 3) 8 and Si 8O 12(CHCH 2) 8

D.A. Wann, C.N. Dickson, P.D. Lickiss, H.E. Robertson, D.W.H. Rankin

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The equilibrium molecular structure of Si 8O 12(OSiMe 3) 8 has been determined in the gas phase by electron diffraction (GED). With OSi-containing substituents on the cage silicon atoms, this molecule contains a moiety, which would, if reproduced in a periodic manner, yield a zeolite-type structure. Extensive ab initio calculations were used to identify two conformers of this molecule, with D 4 and D 2 point-group symmetries; the D 4- symmetric conformer was approximately 1.2 kJ mol -1 lower in energy. With 132 atoms in each conformer, this is one of the largest studies to be undertaken using gas electron diffraction. Semiempirical molecular-dynamics (SE-MD) calculations were used to give amplitudes of vibration, vibrational distance corrections (differences between interatomic distances in the equilibrium structure and the vibrationally averaged distances that are given directly by the diffraction data), and anharmonic constants. The structure of Si 8O 12(CHCH 2) 8 has also been determined by GED. Calculations showed that the vinyl groups are fairly unhindered and rotate between three minimum-energy positions. Ultimately, all possible combinations of the vinyl groups in these low-energy positions were accounted for in the GED model. © 2011 American Chemical Society.

Original language	English
Pages (from-to)	2988-2994
Journal	Inorganic Chemistry
Volume	50
Issue number	7
DOIs	https://doi.org/10.1021/ic102457w
Publication status	Published - 4 Apr 2011

Bibliographical note

Cited By (since 1996):6

Export Date: 1 October 2013

Source: Scopus

CODEN: INOCA

doi: 10.1021/ic102457w

PubMed ID: 21384904

Language of Original Document: English

Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected]

Chemicals/CAS: Gases; Organosilicon Compounds

References: Lickiss, P.D., Rataboul, F., (2008) Adv. Organomet. Chem., 57, p. 1; Cordes, D.B., Lickiss, P.D., Rataboul, F., (2010) Chem. Rev., 110, p. 2081; Quadrelli, E.A., Basset, J.-M., (2010) Coord. Chem. Rev., 254, p. 707; Di Iulio, C., Jones, M.D., Mahon, M.F., Apperley, D.C., (2010) Inorg. Chem., 49, p. 10232; Duchateau, R., (2002) Chem. Rev., 102, p. 3525; Laine, R.M., Sulaiman, S., Brick, C., Roll, M., Tamaki, R., Asuncion, M.Z., Neurock, M., Li, Y., (2010) J. Am. Chem. Soc., 132, p. 3708; Wann, D.A., Reilly, A.M., Rataboul, F., Lickiss, P.D., Rankin, D.W.H., (2009) Z. Naturforsch. B, 64, p. 1269; Wann, D.A., Less, R.J., Rataboul, F., McCaffrey, P.D., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2008) Organometallics, 27, p. 4183; Wann, D.A., Zakharov, A.V., Reilly, A.M., McCaffrey, P.D., Rankin, D.W.H., (2009) J. Phys. Chem. A, 113, p. 9511; Wann, D.A., Rataboul, F., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2009) Dalton Trans., p. 6843; Agaskar, P.A., (1990) Inorg. Chem., 29, p. 1603; Gao, J.-G., Wang, S.-C., Zhang, X.-J., Run, M.-T., (2005) Youjigui Cailiao, 19, p. 5; Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2004) Gaussian 03, , revision C.02; Gaussian, Inc.: Wallingford, CT; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS). (accessed Mar 2011)Krishnan, R., Frisch, M.J., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4244; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Stewart, J.J.P., (2007) J. Mol. Model., 13, p. 1173; Thiel, W.A., Voityuk, A., (1992) Theor. Chim. Acta, 81, p. 391; Vandevondele, J., Krack, M., Mohamed, F., Parrinello, M., Chassaing, T., Hutter, J., (2005) Comput. Phys. Commun., 167, p. 103; http://www.eastchem.ac.uk/rcf, EaStCHEM Research Computing Facility. This facility is partially supported by the eDIKT initiative (http://www.edikt.org)Bussi, G., Donadio, D., Parrinello, M., (2007) J. Chem. Phys., 126, p. 014101; Zakharov, A.V., Personal communicationSipachev, V.A., (1985) THEOCHEM, 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans., p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans., p. 2469; Ross, A.W., Fink, M., Hilderbrandt, R., Wilson, A.J.C., (1992) International Tables for Crystallography, 100, p. 245. , In;, Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands,; Vol., p; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Phys. Chem., 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans., p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502; Baidina, I.A., Podberezskaya, N.V., Alekseev, V.I., Martynova, T.N., Borisov, S.V., Kanev, A.N., (1980) J. Struct. Chem., 20, p. 550; Bonhomme, C., Tolédano, P., Maquet, J., Livage, J., Bonhomme-Coury, L., (1997) J. Chem. Soc., Dalton. Trans., p. 1617; Meier, W.M., Olson, D.H., Baerlocher, C., (1996) Atlas of Zeolite Types, , Elsevier: London; http://www.iza-structure.org, The International Zeolite Association Structure Commission (see)Mellot-Draznieks, C., Girard, S., Férey, G., (2002) J. Am. Chem. Soc., 124, p. 15326. , See:;;, for a discussion of possible structures; Kawahara, K., Hagiwara, Y., Shimojima, A., Kuroda, K., (2008) J. Mater. Chem., 18, p. 3193; Pluth, J.J., Smith, J.V., (1980) J. Am. Chem. Soc., 102, p. 4704; Smolin, Yu.I., Shepelev, Yu.F., Pomes, R., Hoebbel, D., (1979) Kristallografiya, 24, p. 38; Smolin, Yu.I., Shepelev, Yu.F., Butikova, I.K., (1972) Kristallografiya, 17, p. 15; Wiebcke, M., Emmer, J., Felsche, J., Hoebbel, D., Engelhardt, G., (1994) Z. Anorg. Allg. Chem., 620, p. 757; Emmer, J., Wiebcke, M., (1994) J. Chem. Soc., Chem. Commun., p. 2079; Asuncion, M.Z., Hasegawa, I., Kampf, J.W., Laine, R.M., (2005) J. Mater. Chem., 15, p. 2114; Day, V.W., Klemperer, W.G., Mainz, V.V., Millar, D.M., (1985) J. Am. Chem. Soc., 107, p. 8262; Auner, N., Ziemer, B., Herrschaft, B., Ziche, W., John, P., Weis, J., (1999) Eur. J. Inorg. Chem., 7, p. 1087; Slebodnick, C., Angel, R.J., Hanson, B.E., Agaskar, P.A., Soler, T., Falvello, L.R., (2008) Acta Crystallogr., Sect. B: Struct. Sci., 64, p. 330; Clark, J.C., Saengkerdsub, S., Eldridge, G.T., Campana, C., Barnes, C.E., (2006) J. Organomet. Chem., 691, p. 3213

Keywords

organosilicon derivative
article
chemical structure
chemistry
gas
molecular dynamics
quantum theory
Gases
Models, Molecular
Molecular Dynamics Simulation
Molecular Structure
Organosilicon Compounds
Quantum Theory

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10.1021/ic102457w

http://www.scopus.com/inward/record.url?eid=2-s2.0-79953168122&partnerID=40&md5=a3e1cb3991de6d1d1590a27c50a65529

Cite this

@article{04dea007878a4d0fafe795b8ae7ef533,

title = "The gas-phase equilibrium structures of Si 8O 12(OSiMe 3) 8 and Si 8O 12(CHCH 2) 8",

abstract = "The equilibrium molecular structure of Si 8O 12(OSiMe 3) 8 has been determined in the gas phase by electron diffraction (GED). With OSi-containing substituents on the cage silicon atoms, this molecule contains a moiety, which would, if reproduced in a periodic manner, yield a zeolite-type structure. Extensive ab initio calculations were used to identify two conformers of this molecule, with D 4 and D 2 point-group symmetries; the D 4- symmetric conformer was approximately 1.2 kJ mol -1 lower in energy. With 132 atoms in each conformer, this is one of the largest studies to be undertaken using gas electron diffraction. Semiempirical molecular-dynamics (SE-MD) calculations were used to give amplitudes of vibration, vibrational distance corrections (differences between interatomic distances in the equilibrium structure and the vibrationally averaged distances that are given directly by the diffraction data), and anharmonic constants. The structure of Si 8O 12(CHCH 2) 8 has also been determined by GED. Calculations showed that the vinyl groups are fairly unhindered and rotate between three minimum-energy positions. Ultimately, all possible combinations of the vinyl groups in these low-energy positions were accounted for in the GED model. {\textcopyright} 2011 American Chemical Society.",

keywords = "organosilicon derivative, article, chemical structure, chemistry, gas, molecular dynamics, quantum theory, Gases, Models, Molecular, Molecular Dynamics Simulation, Molecular Structure, Organosilicon Compounds, Quantum Theory",

author = "D.A. Wann and C.N. Dickson and P.D. Lickiss and H.E. Robertson and D.W.H. Rankin",

note = "Cited By (since 1996):6 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic102457w PubMed ID: 21384904 Language of Original Document: English Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected] Chemicals/CAS: Gases; Organosilicon Compounds References: Lickiss, P.D., Rataboul, F., (2008) Adv. Organomet. Chem., 57, p. 1; Cordes, D.B., Lickiss, P.D., Rataboul, F., (2010) Chem. Rev., 110, p. 2081; Quadrelli, E.A., Basset, J.-M., (2010) Coord. Chem. Rev., 254, p. 707; Di Iulio, C., Jones, M.D., Mahon, M.F., Apperley, D.C., (2010) Inorg. Chem., 49, p. 10232; Duchateau, R., (2002) Chem. Rev., 102, p. 3525; Laine, R.M., Sulaiman, S., Brick, C., Roll, M., Tamaki, R., Asuncion, M.Z., Neurock, M., Li, Y., (2010) J. Am. Chem. Soc., 132, p. 3708; Wann, D.A., Reilly, A.M., Rataboul, F., Lickiss, P.D., Rankin, D.W.H., (2009) Z. Naturforsch. B, 64, p. 1269; Wann, D.A., Less, R.J., Rataboul, F., McCaffrey, P.D., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2008) Organometallics, 27, p. 4183; Wann, D.A., Zakharov, A.V., Reilly, A.M., McCaffrey, P.D., Rankin, D.W.H., (2009) J. Phys. Chem. A, 113, p. 9511; Wann, D.A., Rataboul, F., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2009) Dalton Trans., p. 6843; Agaskar, P.A., (1990) Inorg. Chem., 29, p. 1603; Gao, J.-G., Wang, S.-C., Zhang, X.-J., Run, M.-T., (2005) Youjigui Cailiao, 19, p. 5; Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2004) Gaussian 03, , revision C.02; Gaussian, Inc.: Wallingford, CT; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS). (accessed Mar 2011)Krishnan, R., Frisch, M.J., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4244; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Stewart, J.J.P., (2007) J. Mol. Model., 13, p. 1173; Thiel, W.A., Voityuk, A., (1992) Theor. Chim. Acta, 81, p. 391; Vandevondele, J., Krack, M., Mohamed, F., Parrinello, M., Chassaing, T., Hutter, J., (2005) Comput. Phys. Commun., 167, p. 103; http://www.eastchem.ac.uk/rcf, EaStCHEM Research Computing Facility. This facility is partially supported by the eDIKT initiative (http://www.edikt.org)Bussi, G., Donadio, D., Parrinello, M., (2007) J. Chem. Phys., 126, p. 014101; Zakharov, A.V., Personal communicationSipachev, V.A., (1985) THEOCHEM, 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans., p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans., p. 2469; Ross, A.W., Fink, M., Hilderbrandt, R., Wilson, A.J.C., (1992) International Tables for Crystallography, 100, p. 245. , In;, Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands,; Vol., p; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Phys. Chem., 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans., p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502; Baidina, I.A., Podberezskaya, N.V., Alekseev, V.I., Martynova, T.N., Borisov, S.V., Kanev, A.N., (1980) J. Struct. Chem., 20, p. 550; Bonhomme, C., Tol{\'e}dano, P., Maquet, J., Livage, J., Bonhomme-Coury, L., (1997) J. Chem. Soc., Dalton. Trans., p. 1617; Meier, W.M., Olson, D.H., Baerlocher, C., (1996) Atlas of Zeolite Types, , Elsevier: London; http://www.iza-structure.org, The International Zeolite Association Structure Commission (see)Mellot-Draznieks, C., Girard, S., F{\'e}rey, G., (2002) J. Am. Chem. Soc., 124, p. 15326. , See:;;, for a discussion of possible structures; Kawahara, K., Hagiwara, Y., Shimojima, A., Kuroda, K., (2008) J. Mater. Chem., 18, p. 3193; Pluth, J.J., Smith, J.V., (1980) J. Am. Chem. Soc., 102, p. 4704; Smolin, Yu.I., Shepelev, Yu.F., Pomes, R., Hoebbel, D., (1979) Kristallografiya, 24, p. 38; Smolin, Yu.I., Shepelev, Yu.F., Butikova, I.K., (1972) Kristallografiya, 17, p. 15; Wiebcke, M., Emmer, J., Felsche, J., Hoebbel, D., Engelhardt, G., (1994) Z. Anorg. Allg. Chem., 620, p. 757; Emmer, J., Wiebcke, M., (1994) J. Chem. Soc., Chem. Commun., p. 2079; Asuncion, M.Z., Hasegawa, I., Kampf, J.W., Laine, R.M., (2005) J. Mater. Chem., 15, p. 2114; Day, V.W., Klemperer, W.G., Mainz, V.V., Millar, D.M., (1985) J. Am. Chem. Soc., 107, p. 8262; Auner, N., Ziemer, B., Herrschaft, B., Ziche, W., John, P., Weis, J., (1999) Eur. J. Inorg. Chem., 7, p. 1087; Slebodnick, C., Angel, R.J., Hanson, B.E., Agaskar, P.A., Soler, T., Falvello, L.R., (2008) Acta Crystallogr., Sect. B: Struct. Sci., 64, p. 330; Clark, J.C., Saengkerdsub, S., Eldridge, G.T., Campana, C., Barnes, C.E., (2006) J. Organomet. Chem., 691, p. 3213",

year = "2011",

month = apr,

day = "4",

doi = "10.1021/ic102457w",

language = "English",

volume = "50",

pages = "2988--2994",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "7",

}

TY - JOUR

T1 - The gas-phase equilibrium structures of Si 8O 12(OSiMe 3) 8 and Si 8O 12(CHCH 2) 8

AU - Wann, D.A.

AU - Dickson, C.N.

AU - Lickiss, P.D.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

N1 - Cited By (since 1996):6 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic102457w PubMed ID: 21384904 Language of Original Document: English Correspondence Address: Wann, D. A.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected] Chemicals/CAS: Gases; Organosilicon Compounds References: Lickiss, P.D., Rataboul, F., (2008) Adv. Organomet. Chem., 57, p. 1; Cordes, D.B., Lickiss, P.D., Rataboul, F., (2010) Chem. Rev., 110, p. 2081; Quadrelli, E.A., Basset, J.-M., (2010) Coord. Chem. Rev., 254, p. 707; Di Iulio, C., Jones, M.D., Mahon, M.F., Apperley, D.C., (2010) Inorg. Chem., 49, p. 10232; Duchateau, R., (2002) Chem. Rev., 102, p. 3525; Laine, R.M., Sulaiman, S., Brick, C., Roll, M., Tamaki, R., Asuncion, M.Z., Neurock, M., Li, Y., (2010) J. Am. Chem. Soc., 132, p. 3708; Wann, D.A., Reilly, A.M., Rataboul, F., Lickiss, P.D., Rankin, D.W.H., (2009) Z. Naturforsch. B, 64, p. 1269; Wann, D.A., Less, R.J., Rataboul, F., McCaffrey, P.D., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2008) Organometallics, 27, p. 4183; Wann, D.A., Zakharov, A.V., Reilly, A.M., McCaffrey, P.D., Rankin, D.W.H., (2009) J. Phys. Chem. A, 113, p. 9511; Wann, D.A., Rataboul, F., Reilly, A.M., Robertson, H.E., Lickiss, P.D., Rankin, D.W.H., (2009) Dalton Trans., p. 6843; Agaskar, P.A., (1990) Inorg. Chem., 29, p. 1603; Gao, J.-G., Wang, S.-C., Zhang, X.-J., Run, M.-T., (2005) Youjigui Cailiao, 19, p. 5; Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery Jr., J.A., Pople, J.A., (2004) Gaussian 03, , revision C.02; Gaussian, Inc.: Wallingford, CT; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS). (accessed Mar 2011)Krishnan, R., Frisch, M.J., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4244; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Stewart, J.J.P., (2007) J. Mol. Model., 13, p. 1173; Thiel, W.A., Voityuk, A., (1992) Theor. Chim. Acta, 81, p. 391; Vandevondele, J., Krack, M., Mohamed, F., Parrinello, M., Chassaing, T., Hutter, J., (2005) Comput. Phys. Commun., 167, p. 103; http://www.eastchem.ac.uk/rcf, EaStCHEM Research Computing Facility. This facility is partially supported by the eDIKT initiative (http://www.edikt.org)Bussi, G., Donadio, D., Parrinello, M., (2007) J. Chem. Phys., 126, p. 014101; Zakharov, A.V., Personal communicationSipachev, V.A., (1985) THEOCHEM, 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Fleischer, H., Wann, D.A., Hinchley, S.L., Borisenko, K.B., Lewis, J.R., Mawhorter, R.J., Robertson, H.E., Rankin, D.W.H., (2005) Dalton Trans., p. 3221; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans., p. 2469; Ross, A.W., Fink, M., Hilderbrandt, R., Wilson, A.J.C., (1992) International Tables for Crystallography, 100, p. 245. , In;, Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands,; Vol., p; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J. Phys. Chem., 100, p. 12280; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J. Chem. Soc., Dalton Trans., p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Hamilton, W.C., (1965) Acta Crystallogr., 18, p. 502; Baidina, I.A., Podberezskaya, N.V., Alekseev, V.I., Martynova, T.N., Borisov, S.V., Kanev, A.N., (1980) J. Struct. Chem., 20, p. 550; Bonhomme, C., Tolédano, P., Maquet, J., Livage, J., Bonhomme-Coury, L., (1997) J. Chem. Soc., Dalton. Trans., p. 1617; Meier, W.M., Olson, D.H., Baerlocher, C., (1996) Atlas of Zeolite Types, , Elsevier: London; http://www.iza-structure.org, The International Zeolite Association Structure Commission (see)Mellot-Draznieks, C., Girard, S., Férey, G., (2002) J. Am. Chem. Soc., 124, p. 15326. , See:;;, for a discussion of possible structures; Kawahara, K., Hagiwara, Y., Shimojima, A., Kuroda, K., (2008) J. Mater. Chem., 18, p. 3193; Pluth, J.J., Smith, J.V., (1980) J. Am. Chem. Soc., 102, p. 4704; Smolin, Yu.I., Shepelev, Yu.F., Pomes, R., Hoebbel, D., (1979) Kristallografiya, 24, p. 38; Smolin, Yu.I., Shepelev, Yu.F., Butikova, I.K., (1972) Kristallografiya, 17, p. 15; Wiebcke, M., Emmer, J., Felsche, J., Hoebbel, D., Engelhardt, G., (1994) Z. Anorg. Allg. Chem., 620, p. 757; Emmer, J., Wiebcke, M., (1994) J. Chem. Soc., Chem. Commun., p. 2079; Asuncion, M.Z., Hasegawa, I., Kampf, J.W., Laine, R.M., (2005) J. Mater. Chem., 15, p. 2114; Day, V.W., Klemperer, W.G., Mainz, V.V., Millar, D.M., (1985) J. Am. Chem. Soc., 107, p. 8262; Auner, N., Ziemer, B., Herrschaft, B., Ziche, W., John, P., Weis, J., (1999) Eur. J. Inorg. Chem., 7, p. 1087; Slebodnick, C., Angel, R.J., Hanson, B.E., Agaskar, P.A., Soler, T., Falvello, L.R., (2008) Acta Crystallogr., Sect. B: Struct. Sci., 64, p. 330; Clark, J.C., Saengkerdsub, S., Eldridge, G.T., Campana, C., Barnes, C.E., (2006) J. Organomet. Chem., 691, p. 3213

PY - 2011/4/4

Y1 - 2011/4/4

N2 - The equilibrium molecular structure of Si 8O 12(OSiMe 3) 8 has been determined in the gas phase by electron diffraction (GED). With OSi-containing substituents on the cage silicon atoms, this molecule contains a moiety, which would, if reproduced in a periodic manner, yield a zeolite-type structure. Extensive ab initio calculations were used to identify two conformers of this molecule, with D 4 and D 2 point-group symmetries; the D 4- symmetric conformer was approximately 1.2 kJ mol -1 lower in energy. With 132 atoms in each conformer, this is one of the largest studies to be undertaken using gas electron diffraction. Semiempirical molecular-dynamics (SE-MD) calculations were used to give amplitudes of vibration, vibrational distance corrections (differences between interatomic distances in the equilibrium structure and the vibrationally averaged distances that are given directly by the diffraction data), and anharmonic constants. The structure of Si 8O 12(CHCH 2) 8 has also been determined by GED. Calculations showed that the vinyl groups are fairly unhindered and rotate between three minimum-energy positions. Ultimately, all possible combinations of the vinyl groups in these low-energy positions were accounted for in the GED model. © 2011 American Chemical Society.

AB - The equilibrium molecular structure of Si 8O 12(OSiMe 3) 8 has been determined in the gas phase by electron diffraction (GED). With OSi-containing substituents on the cage silicon atoms, this molecule contains a moiety, which would, if reproduced in a periodic manner, yield a zeolite-type structure. Extensive ab initio calculations were used to identify two conformers of this molecule, with D 4 and D 2 point-group symmetries; the D 4- symmetric conformer was approximately 1.2 kJ mol -1 lower in energy. With 132 atoms in each conformer, this is one of the largest studies to be undertaken using gas electron diffraction. Semiempirical molecular-dynamics (SE-MD) calculations were used to give amplitudes of vibration, vibrational distance corrections (differences between interatomic distances in the equilibrium structure and the vibrationally averaged distances that are given directly by the diffraction data), and anharmonic constants. The structure of Si 8O 12(CHCH 2) 8 has also been determined by GED. Calculations showed that the vinyl groups are fairly unhindered and rotate between three minimum-energy positions. Ultimately, all possible combinations of the vinyl groups in these low-energy positions were accounted for in the GED model. © 2011 American Chemical Society.

KW - organosilicon derivative

KW - article

KW - chemical structure

KW - chemistry

KW - gas

KW - molecular dynamics

KW - quantum theory

KW - Gases

KW - Models, Molecular

KW - Molecular Dynamics Simulation

KW - Molecular Structure

KW - Organosilicon Compounds

KW - Quantum Theory

U2 - 10.1021/ic102457w

DO - 10.1021/ic102457w

M3 - Article

SN - 0020-1669

VL - 50

SP - 2988

EP - 2994

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

ER -