Dimethylalkoxygallanes:  monomeric versus dimeric gas-phase structures

C.E. Knapp; D.A. Wann; A. Bil; J.T. Schirlin; H.E. Robertson; P.F. McMillan; D.W.H. Rankin; C.J. Carmalt

doi:10.1021/ic202775x

Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures

C.E. Knapp, D.A. Wann, A. Bil, J.T. Schirlin, H.E. Robertson, P.F. McMillan, D.W.H. Rankin, C.J. Carmalt

Chemistry

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

Abstract

The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me 2Ga(OR)] 2 have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me 2Ga(OCH 2CH 2NMe 2)] 2 (1) and [Me 2Ga(OCH 2CH 2OMe)] 2 (2) adopt dimeric structures, although only the monomeric forms [Me 2Ga(OCH 2CH 2NMe 2)] (1a) and [Me 2Ga(OCH 2CH 2OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me 2Ga(O tBu)] 2 (3) was also studied by gas electron diffraction. In contrast to 1 and 2, compound 3 is dimeric in the gas phase, as well as in the solid state. The gas-phase structures of 1a and 2a exhibit five-membered rings formed by a dative bond between Ga and the donor atom (N or O) from the donor-functionalized alkoxide. In 3 there is no possibility of a monomeric structure being stabilized by the formation of such a dative bond since only a monofunctional alkoxide is present in the molecule. © 2012 American Chemical Society.

Original language	English
Pages (from-to)	3324-3331
Journal	Inorganic Chemistry
Volume	51
Issue number	5
DOIs	https://doi.org/10.1021/ic202775x
Publication status	Published - 5 Mar 2012

Bibliographical note

Cited By (since 1996):1

Export Date: 1 October 2013

Source: Scopus

CODEN: INOCA

doi: 10.1021/ic202775x

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]

References: Carmalt, C.J., King, S.J., (2006) Coord. Chem. Rev., 250, p. 682; Bloor, L., Pugh, D., Carmalt, C.J., (2011) Coord. Chem. Rev., 255, p. 1293; Coates, G.E., Hayter, R.G., (1953) J. Chem. Soc., p. 2519; Schwering, H.-U., Jungk, E., Weidlein, J., (1975) J. Organomet. Chem., 91, p. 4; Basharat, S., Carmalt, C.J., King, S.J., Peters, E.S., Tocher, D.A., (2004) Dalton Trans., p. 3475; Mîinea, L., Suh, S., Bott, S.G., Liu, J.-R., Chu, W.-K., Hoffman, D.M., (1999) J. Mater. Chem., 9, p. 929; Valet, M., Hoffman, D.M., (2001) Chem. Mater., 13, p. 2135; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2008) J. Organomet. Chem., 693, p. 1787; Knapp, C.E., Pemberton, L., Carmalt, C.J., Pugh, D., McMillan, P.F., Barnett, S.A., Tocher, D.A., (2010) Main Group Chem., 9, p. 31; Knapp, C.E., Pugh, D., McMillan, P.F., Parkin, I.P., Carmalt, C.J., (2011) Inorg. Chem., 50, p. 9491; Basharat, S., Carmalt, C.J., Binions, R., Palgrave, R., Parkin, I.P., (2008) Dalton Trans., p. 591; Basharat, S., Knapp, C.E., Carmalt, C.J., Barnett, S.A., Tocher, D.A., (2008) New J. Chem., 32, p. 1513; Suh, S., Hoffman, D.M., (2000) J. Am. Chem. Soc., 122, p. 9396; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2007) Inorg. Chem., 46, p. 9473; Knapp, C.E., Hyett, G., Parkin, I.P., Carmalt, C.J., (2011) Chem. Mater., 23, p. 1719; Knapp, C.E., Kafizas, A., Parkin, I.P., Carmalt, C.J., (2011) J. Mater. Chem., 21, p. 12644; Fleischer, M., Meixner, H., (1993) Sens. Actuators, B, 13, p. 259; Binions, R., Carmalt, C.J., Parkin, I.P., (2007) Meas. Sci. Technol., 18, p. 190; Knapp, C.E., Carmalt, C.J., McMillan, P.F., Wann, D.A., Robertson, H.E., Rankin, D.W.H., (2008) Dalton Trans., p. 6880; Davis, M.J., Pemble, M.E., (1999) J. Phys.-Paris IV, 9, p. 49; Vemardou, D., Pemble, M.E., Sheel, D.W., (2007) Thin Solid Films, 515, p. 8768; Vernardou, D., Pemble, M.E., Sheel, D.W., (2008) Thin Solid Films, 516, p. 4502; Holdsworth, R.J., Martin, P.A., Raisbeck, D., Rivero, J., Sanders, H.E., Sheel, D.W., Pemble, M.E., (2001) Chem. Vap. Deposition, 7, p. 39; Gould, B.J., Povey, I.M., Pemble, M.E., Flavell, W.R., (1994) J. Mater. Chem., 4, p. 1815; Schumann, H., Frick, M., Heymer, B., Girgsdies, F., (1996) J. Organomet. Chem., 512, p. 117; Rettig, S.J., Storr, A., Trotter, J., (1975) Can. J. Chem., 53, p. 58; Schmidbaur, H., (1965) Angew. Chem., Int. Ed. Engl., 4, p. 152; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS). URLFrisch, 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; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J. Am. Chem. 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Soc., Dalton Trans., p. 954; Schirlin, J.T., (2004), Ph.D. Thesis, University of Edinburgh, Edinburgh, U.KFleischer, 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., (1992) International Tables for Crystallography, 100, p. 245. , In; Wilson, A. J. C. Kluwer Academic Publishers: Dordrecht, The Netherlands, Vol; 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. 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10.1021/ic202775x

http://www.scopus.com/inward/record.url?eid=2-s2.0-84857873154&partnerID=40&md5=69a8ced075ce133500195c55421fa0b6

TRED: Towards molecular movies:exploring reaction dynamics using electron diffraction
Wann, D. A.
EPSRC
1/09/13 → 31/07/15
Project: Research project (funded) › Research

Cite this

@article{f2e6b12a6dff42deb74f12c5aa05bb20,

title = "Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures",

abstract = "The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me 2Ga(OR)] 2 have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me 2Ga(OCH 2CH 2NMe 2)] 2 (1) and [Me 2Ga(OCH 2CH 2OMe)] 2 (2) adopt dimeric structures, although only the monomeric forms [Me 2Ga(OCH 2CH 2NMe 2)] (1a) and [Me 2Ga(OCH 2CH 2OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me 2Ga(O tBu)] 2 (3) was also studied by gas electron diffraction. In contrast to 1 and 2, compound 3 is dimeric in the gas phase, as well as in the solid state. The gas-phase structures of 1a and 2a exhibit five-membered rings formed by a dative bond between Ga and the donor atom (N or O) from the donor-functionalized alkoxide. In 3 there is no possibility of a monomeric structure being stabilized by the formation of such a dative bond since only a monofunctional alkoxide is present in the molecule. {\textcopyright} 2012 American Chemical Society.",

author = "C.E. Knapp and D.A. Wann and A. Bil and J.T. Schirlin and H.E. Robertson and P.F. McMillan and D.W.H. Rankin and C.J. Carmalt",

note = "Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic202775x 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] References: Carmalt, C.J., King, S.J., (2006) Coord. Chem. Rev., 250, p. 682; Bloor, L., Pugh, D., Carmalt, C.J., (2011) Coord. Chem. Rev., 255, p. 1293; Coates, G.E., Hayter, R.G., (1953) J. Chem. Soc., p. 2519; Schwering, H.-U., Jungk, E., Weidlein, J., (1975) J. Organomet. Chem., 91, p. 4; Basharat, S., Carmalt, C.J., King, S.J., Peters, E.S., Tocher, D.A., (2004) Dalton Trans., p. 3475; M{\^i}inea, L., Suh, S., Bott, S.G., Liu, J.-R., Chu, W.-K., Hoffman, D.M., (1999) J. Mater. Chem., 9, p. 929; Valet, M., Hoffman, D.M., (2001) Chem. Mater., 13, p. 2135; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2008) J. Organomet. Chem., 693, p. 1787; Knapp, C.E., Pemberton, L., Carmalt, C.J., Pugh, D., McMillan, P.F., Barnett, S.A., Tocher, D.A., (2010) Main Group Chem., 9, p. 31; Knapp, C.E., Pugh, D., McMillan, P.F., Parkin, I.P., Carmalt, C.J., (2011) Inorg. Chem., 50, p. 9491; Basharat, S., Carmalt, C.J., Binions, R., Palgrave, R., Parkin, I.P., (2008) Dalton Trans., p. 591; Basharat, S., Knapp, C.E., Carmalt, C.J., Barnett, S.A., Tocher, D.A., (2008) New J. Chem., 32, p. 1513; Suh, S., Hoffman, D.M., (2000) J. Am. Chem. Soc., 122, p. 9396; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2007) Inorg. Chem., 46, p. 9473; Knapp, C.E., Hyett, G., Parkin, I.P., Carmalt, C.J., (2011) Chem. Mater., 23, p. 1719; Knapp, C.E., Kafizas, A., Parkin, I.P., Carmalt, C.J., (2011) J. Mater. Chem., 21, p. 12644; Fleischer, M., Meixner, H., (1993) Sens. Actuators, B, 13, p. 259; Binions, R., Carmalt, C.J., Parkin, I.P., (2007) Meas. Sci. Technol., 18, p. 190; Knapp, C.E., Carmalt, C.J., McMillan, P.F., Wann, D.A., Robertson, H.E., Rankin, D.W.H., (2008) Dalton Trans., p. 6880; Davis, M.J., Pemble, M.E., (1999) J. Phys.-Paris IV, 9, p. 49; Vemardou, D., Pemble, M.E., Sheel, D.W., (2007) Thin Solid Films, 515, p. 8768; Vernardou, D., Pemble, M.E., Sheel, D.W., (2008) Thin Solid Films, 516, p. 4502; Holdsworth, R.J., Martin, P.A., Raisbeck, D., Rivero, J., Sanders, H.E., Sheel, D.W., Pemble, M.E., (2001) Chem. Vap. Deposition, 7, p. 39; Gould, B.J., Povey, I.M., Pemble, M.E., Flavell, W.R., (1994) J. Mater. Chem., 4, p. 1815; Schumann, H., Frick, M., Heymer, B., Girgsdies, F., (1996) J. Organomet. Chem., 512, p. 117; Rettig, S.J., Storr, A., Trotter, J., (1975) Can. J. Chem., 53, p. 58; Schmidbaur, H., (1965) Angew. Chem., Int. Ed. Engl., 4, p. 152; http://www.nsccs.ac.uk, National Service for Computational Chemistry Software (NSCCS). URLFrisch, 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; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J. Am. Chem. Soc., 102, p. 939; Gordon, M.S., Binkley, J.S., Pople, J.A., Pietro, W.J., Hehre, W.J., (1982) J. Am. Chem. Soc., 104, p. 2797; Pietro, W.J., Francl, M.M., Hehre, W.J., Defrees, D.J., Pople, J.A., Binkley, J.S., (1982) J. Am. Chem. Soc., 104, p. 5039; Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257; Hariharan, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, p. 213; Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163; M{\o}ller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B, 37, p. 785; Bader, R.F.W., (1994) Atoms in Molecules: A Quantum Theory, , Oxford University Press: Oxford, U.K; Bader, R.F.W., (1991) Chem. Rev., 91, p. 893; Bader, R.F.W., (1998) J. Phys. Chem. A, 102, p. 7314; Keith, T.A., (2011) AIMAll, , (version 11.03.14); TK Gristmill Software: Overland Park, KS; Becke, A.D., Edgecombe, K.E., (1990) J. Chem. Phys., 92, p. 5397; Silvi, B., Savin, A., (1994) Nature, 371, p. 683; Savin, A., Nesper, R., Wengert, S., F{\"a}ssler, T., (1997) Angew. Chem., Int. Ed. Engl., 36, p. 1808; Noury, S., Krokidis, X., Fuster, F., Silvi, B., (1999) Comput. Chem., 23, p. 597; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Schirlin, J.T., (2004), Ph.D. Thesis, University of Edinburgh, Edinburgh, U.KFleischer, 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., (1992) International Tables for Crystallography, 100, p. 245. , In; Wilson, A. J. C. Kluwer Academic Publishers: Dordrecht, The Netherlands, Vol; 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; Chi, Y., Chou, T.-Y., Wang, Y.-J., Huang, S.-F., Carty, A.J., Scoles, L., Udachin, K.A., Lee, G.-H., (2004) Organometallics, 23, p. 95; Power, M.B., Cleaver, W.M., Apblett, A.W., Barron, A.R., Ziller, J.W., (1992) Polyhedron, 11, p. 477; Veith, M., Faber, S., Wolfanger, H., Huch, V., (1996) Chem. Ber., 129, p. 381; Bader, R.F.W., Nguyen-Danf, T.T., Tal, Y., (1981) Rep. Prog. Phys., 44, p. 893",

year = "2012",

month = mar,

day = "5",

doi = "10.1021/ic202775x",

language = "English",

volume = "51",

pages = "3324--3331",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Dimethylalkoxygallanes

T2 - monomeric versus dimeric gas-phase structures

AU - Knapp, C.E.

AU - Wann, D.A.

AU - Bil, A.

AU - Schirlin, J.T.

AU - Robertson, H.E.

AU - McMillan, P.F.

AU - Rankin, D.W.H.

AU - Carmalt, C.J.

N1 - Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic202775x 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] References: Carmalt, C.J., King, S.J., (2006) Coord. Chem. Rev., 250, p. 682; Bloor, L., Pugh, D., Carmalt, C.J., (2011) Coord. Chem. Rev., 255, p. 1293; Coates, G.E., Hayter, R.G., (1953) J. Chem. Soc., p. 2519; Schwering, H.-U., Jungk, E., Weidlein, J., (1975) J. Organomet. Chem., 91, p. 4; Basharat, S., Carmalt, C.J., King, S.J., Peters, E.S., Tocher, D.A., (2004) Dalton Trans., p. 3475; Mîinea, L., Suh, S., Bott, S.G., Liu, J.-R., Chu, W.-K., Hoffman, D.M., (1999) J. Mater. Chem., 9, p. 929; Valet, M., Hoffman, D.M., (2001) Chem. Mater., 13, p. 2135; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2008) J. Organomet. Chem., 693, p. 1787; Knapp, C.E., Pemberton, L., Carmalt, C.J., Pugh, D., McMillan, P.F., Barnett, S.A., Tocher, D.A., (2010) Main Group Chem., 9, p. 31; Knapp, C.E., Pugh, D., McMillan, P.F., Parkin, I.P., Carmalt, C.J., (2011) Inorg. Chem., 50, p. 9491; Basharat, S., Carmalt, C.J., Binions, R., Palgrave, R., Parkin, I.P., (2008) Dalton Trans., p. 591; Basharat, S., Knapp, C.E., Carmalt, C.J., Barnett, S.A., Tocher, D.A., (2008) New J. Chem., 32, p. 1513; Suh, S., Hoffman, D.M., (2000) J. Am. Chem. Soc., 122, p. 9396; Basharat, S., Carmalt, C.J., Barnett, S.A., Tocher, D.A., Davies, H.O., (2007) Inorg. Chem., 46, p. 9473; Knapp, C.E., Hyett, G., Parkin, I.P., Carmalt, C.J., (2011) Chem. Mater., 23, p. 1719; Knapp, C.E., Kafizas, A., Parkin, I.P., Carmalt, C.J., (2011) J. Mater. Chem., 21, p. 12644; Fleischer, M., Meixner, H., (1993) Sens. Actuators, B, 13, p. 259; Binions, R., Carmalt, C.J., Parkin, I.P., (2007) Meas. Sci. 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PY - 2012/3/5

Y1 - 2012/3/5

N2 - The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me 2Ga(OR)] 2 have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me 2Ga(OCH 2CH 2NMe 2)] 2 (1) and [Me 2Ga(OCH 2CH 2OMe)] 2 (2) adopt dimeric structures, although only the monomeric forms [Me 2Ga(OCH 2CH 2NMe 2)] (1a) and [Me 2Ga(OCH 2CH 2OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me 2Ga(O tBu)] 2 (3) was also studied by gas electron diffraction. In contrast to 1 and 2, compound 3 is dimeric in the gas phase, as well as in the solid state. The gas-phase structures of 1a and 2a exhibit five-membered rings formed by a dative bond between Ga and the donor atom (N or O) from the donor-functionalized alkoxide. In 3 there is no possibility of a monomeric structure being stabilized by the formation of such a dative bond since only a monofunctional alkoxide is present in the molecule. © 2012 American Chemical Society.

AB - The molecular structures of the vapors produced on heating dimethylalkoxygallanes of the type [Me 2Ga(OR)] 2 have been determined by gas electron diffraction and ab initio molecular orbital calculations. In the solid state [Me 2Ga(OCH 2CH 2NMe 2)] 2 (1) and [Me 2Ga(OCH 2CH 2OMe)] 2 (2) adopt dimeric structures, although only the monomeric forms [Me 2Ga(OCH 2CH 2NMe 2)] (1a) and [Me 2Ga(OCH 2CH 2OMe)] (2a) were observed in the gas phase. For comparison the structure of the vapor produced on heating [Me 2Ga(O tBu)] 2 (3) was also studied by gas electron diffraction. In contrast to 1 and 2, compound 3 is dimeric in the gas phase, as well as in the solid state. The gas-phase structures of 1a and 2a exhibit five-membered rings formed by a dative bond between Ga and the donor atom (N or O) from the donor-functionalized alkoxide. In 3 there is no possibility of a monomeric structure being stabilized by the formation of such a dative bond since only a monofunctional alkoxide is present in the molecule. © 2012 American Chemical Society.

U2 - 10.1021/ic202775x

DO - 10.1021/ic202775x

M3 - Article

SN - 0020-1669

VL - 51

SP - 3324

EP - 3331

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

Dimethylalkoxygallanes: monomeric versus dimeric gas-phase structures

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