Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation

A. Keys; P.T. Brain; C.A. Morrison; R.L. Callender; B.A. Smart; D.A. Wann; H.E. Robertson; D.W.H. Rankin; A.R. Barron

doi:10.1039/b714168h

Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation

A. Keys, P.T. Brain, C.A. Morrison, R.L. Callender, B.A. Smart, D.A. Wann, H.E. Robertson, D.W.H. Rankin, A.R. Barron

Chemistry

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

Abstract

The gas-phase structures of Al(But)3 and Ga(Bu t)3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (rh1) include rAl-C = 2.008(2) and rGa-C = 2.032(2). For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(But)3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(But)3 with those of Al(But)3 and Ga(But)3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two. This journal is © The Royal Society of Chemistry.

Original language	Undefined/Unknown
Pages (from-to)	404-410
Number of pages	7
Journal	Dalton Transactions
Issue number	3
DOIs	https://doi.org/10.1039/b714168h
Publication status	Published - 2008

Bibliographical note

Cited By (since 1996):1

Export Date: 1 October 2013

Source: Scopus

doi: 10.1039/b714168h

PubMed ID: 18411850

Language of Original Document: English

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

Chemicals/CAS: aluminum, 7429-90-5; butane, 106-97-8; gallium, 7440-55-3; indium, 7440-74-6; Aluminum, 7429-90-5; Butanes; Gallium, 7440-55-3; Gases; Indium, 7440-74-6; Organometallic Compounds

References: Barron, A.R., (1993) Chem. Soc. Rev., p. 93; Barron, A.R., (1993) Commun. Inorg. Chem., 14, p. 123; Barron, A.R., (1995) Macromol. Symp., 97, p. 15; Barron, A.R., (1995) Adv. Mater. Opt. Electron., 5, p. 245; Tolman, C.A., (1977) Chem. Rev., 77, p. 313; Landry, C.C., Harlan, C.J., Bott, S.G., Barron, A.R., (1995) Angew. Chem., Int. Ed. Engl., 34, p. 1201; McMahon, C.N., Bott, S.G., Barron, A.R., (1997) J. Chem. Soc., Dalton Trans., p. 3129; Francis, J.A., McMahon, C.N., Bott, S.G., Barron, A.R., (1999) Organometallics, 18, p. 4399; MacInnes, A.N., Power, M.B., Hepp, A.F., Barron, A.R., (1993) J. Organomet. Chem., 449, p. 95; Landry, C.C., Haynes, A., Barron, A.R., Haiduc, I., Silvestru, C., (1996) Polyhedron, 15, p. 391; Cleaver, W.M., Barron, A.R., McGuffrey, A.R., Bott, S.G., (1994) Polyhedron, 13, p. 2831; Gillan, E.G., Bott, S.G., Barron, A.R., (1997) Chem. Mater., 9, p. 796; Fletcher, D.A., McMeeking, R.F., Parkin, D., Chemical Database Service at Daresbury Laboratory (1996) J. Chem. Inf. Comput. Sci., 36, p. 746; Woski, M., Mitzel, N.W., (2004) Z. Naturforsch., B: Chem. Sci., 59, p. 269; Cowley, A.R., Downs, A.J., Marchant, S., MacRae, V.A., Taylor, R.A., Parsons, S., (2005) Organometallics, 24, p. 5702; Kuczkowski, A., Schulz, S., Nieger, M., (2004) Appl. Organomet. Chem., 18, p. 244; Uhl, W., Emden, C.H., Geiseler, G., Harms, K., (2003) Z. Anorg. Allg. Chem., 629, p. 2157; Uhl, W., (1989) Z. Anorg. Allg. Chem., 570, p. 37; Lehmkuhl, H., Olbrysch, O., Nehl, H., (1973) Liebigs Ann. Chem., p. 708; Lehmkuhl, H., Olbrysch, O., (1973) Liebigs Ann. Chem., p. 715; Kovar, R.A., Derr, H., Brandau, D., Callaway, J.O., (1975) Inorg. Chem., 14, p. 2809; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; 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 In, R., (1992) International Tables for Crystallography, Ed., , http://www.nsccs.ac.uk, A. J. C. Wilson, Kluwer Academic Publishers, Dordrecht, The Netherlands, p. 245 EPSRC National Service for Computational Chemistry Software. URL; 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.01, , 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; 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; Huzinaga, S., Klobukowski, M., (1988) THEOCHEM, 167, p. 1; Sipachev, V.A., (1985) THEOCHEM, 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Hegarty, D., Robb, M.A., (1979) Mol. Phys., 38, p. 1795; Eade, R.H.E., Robb, M.A., (1981) Chem. Phys. Lett., 83, p. 362; Schlegel, H.B., Robb, M.A., (1982) Chem. Phys. Lett., 93, p. 43; Bernardi, F., Bottini, A., McDougall, J.J.W., Robb, M.A., Schlegel, H.B., (1984) Far. Symp. Chem. Soc., 19, p. 137; Yamamoto, N., Vreven, T., Robb, M.A., Frisch, M.J., Schlegel, H.B., (1996) Chem. Phys. Lett., 250, p. 373; Frisch, M.J., Ragazos, I.N., Robb, M.A., Schlegel, H.B., (1992) Chem. Phys. Lett., 189, p. 524; Stratmann, R.E., Scuseria, G.E., Frisch, M.J., (1998) J. Chem. Phys., 109, p. 8218; Bauernschmitt, R., Ahlrichs, R., (1996) Chem. Phys. Lett., 256, p. 454; Casida, M.E., Jamorski, C., Casida, K.C., Salahub, D.R., (1998) J. Chem. Phys., 108, p. 4439; 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; Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys., 82, p. 270; Wadt, W.R., Hay, P.J., (1985) J. Chem. Phys., 82, p. 284; Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys., 82, p. 299; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Almenningen, A., Halvorsen, S., Haaland, A., (1971) Acta Chem. Scand., 25, p. 1937; Beagley, B., Schmidling, D.G., Steer, I.A., (1974) J. Mol. Struct., 21, p. 437; Rahman, A.F.M.M., Siddiqul, K.F., Oliver, J.P., (1982) Organometallics, 1, p. 881; Pauling, L., Laubengayer, A.W., (1941) J. Am. Chem. Soc., 63, p. 480; Barbe, G., Hencher, J.L., Shen, Q., Tuck, D.G., (1974) Can. J. Chem., 52, p. 3936; Jerius, J.J., Hahn, J.M., Rahman, A.F.M.M., Mols, O., Ilsey, W.H., Oliver, J.P., (1986) Organometallics, 5, p. 1812; Beachley Jr. O., T., Churchill, M.R., Pazik, J.C., Ziller, J.W., (1986) Organometallics, 5, p. 1817; Malone, J.F., McDonald, W.S., (1970) J. Chem. Soc. A, p. 3363; Harlan, C.J., Bott, S.G., Barron, A.R., (1995) J. Am. Chem. Soc., 117, p. 6465; McMahon, C.N., Barron, A.R., (1997) J. Chem. Crystallogr., 27, p. 171; Aitken, C.L., Barron, A.R., (1999) J. Chem. Crystallogr., 29, p. 993; Keys, A., Barbarich, T., Bott, S.G., Barron, A.R., (2000) J. Chem. Soc., Dalton Trans., p. 577; Bradley, D.C., Frigo, D.M., Hursthouse, M.B., Hussain, B., (1988) Organometallics, 7, p. 1112; Cleaver Phd Thesis, W.M., (1994), Harvard UniversityLeman, J.T., Barron, A.R., (1989) Organometallics, 8, p. 2214; Carty, A.J., Gynane, M.J., Lappert, M.F., Miles, S.J., Singh, A., Taylor, N.J., (1980) Inorg. Chem., 19, p. 3637; Brookhart, M., Green, M.L.H., (1983) J. Organomet. Chem., 250, p. 395; McDaniel, A.H., Allendorf, M.D., (2000) Chem. Mater., 12, p. 450; Allendorf, M.D., Melius, C.F., Bauschlicher, C.W., (1999) J. Phys. IV, 9, p. 8. , -23; Russell, D.K., (1996) Chem. Vap. Deposition, 2, p. 223; Jacko, M.G., Price, S.J.W., (1964) Can. J. Chem., 42, p. 1198; Clark, W.D., Price, S.J.W., (1968) Can. J. Chem., 46, p. 1633; Zhang, Y., Beuermann, T., Stuke, M., (1989) Appl. Phys. B, 48, p. 97; Zhang, Y., Stuke, M., (1988) Chemtronics, 3, p. 230; Cleaver, W.M., Barron, A.R., Zhang, Y., Stuke, M., (1992) Appl. Surf. Sci., 54, p. 8; Zhang, Y., Cleaver, W.M., Stuke, M., Barron, A.R., (1992) Appl. Phys. A, 55, p. 261

Keywords

Aluminum compounds
Charge transfer
Electron diffraction
Gallium compounds
Ligands
Molecular interactions
Photodissociation
Interligand interactions
Ligand orientations
Monomeric units
Molecular structure
aluminum
butane
gallium
indium
organometallic compound
article
chemical model
chemical structure
chemistry
computer simulation
electron
gas
phase transition
photochemistry
quantum theory
X ray crystallography
Aluminum
Butanes
Computer Simulation
Crystallography, X-Ray
Electrons
Gallium
Gases
Indium
Models, Chemical
Models, Molecular
Organometallic Compounds
Phase Transition
Photochemistry
Quantum Theory

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10.1039/b714168h

http://www.scopus.com/inward/record.url?eid=2-s2.0-37849011726&partnerID=40&md5=10f55bb995fa760111070d451bc9f14a

Cite this

Keys, A., Brain, P. T., Morrison, C. A., Callender, R. L., Smart, B. A., Wann, D. A., Robertson, H. E., Rankin, D. W. H., & Barron, A. R. (2008). Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation. Dalton Transactions, (3), 404-410. https://doi.org/10.1039/b714168h

@article{439170b5bb6d46f993d8486799e9cb5c,

title = "Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation",

abstract = "The gas-phase structures of Al(But)3 and Ga(Bu t)3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (rh1) include rAl-C = 2.008(2) and rGa-C = 2.032(2). For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(But)3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(But)3 with those of Al(But)3 and Ga(But)3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two. This journal is {\textcopyright} The Royal Society of Chemistry.",

keywords = "Aluminum compounds, Charge transfer, Electron diffraction, Gallium compounds, Ligands, Molecular interactions, Photodissociation, Interligand interactions, Ligand orientations, Monomeric units, Molecular structure, aluminum, butane, gallium, indium, organometallic compound, article, chemical model, chemical structure, chemistry, computer simulation, electron, gas, phase transition, photochemistry, quantum theory, X ray crystallography, Aluminum, Butanes, Computer Simulation, Crystallography, X-Ray, Electrons, Gallium, Gases, Indium, Models, Chemical, Models, Molecular, Organometallic Compounds, Phase Transition, Photochemistry, Quantum Theory",

author = "A. Keys and P.T. Brain and C.A. Morrison and R.L. Callender and B.A. Smart and D.A. Wann and H.E. Robertson and D.W.H. Rankin and A.R. Barron",

note = "Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus doi: 10.1039/b714168h PubMed ID: 18411850 Language of Original Document: English Correspondence Address: Rankin, D.W.H.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: [email protected] Chemicals/CAS: aluminum, 7429-90-5; butane, 106-97-8; gallium, 7440-55-3; indium, 7440-74-6; Aluminum, 7429-90-5; Butanes; Gallium, 7440-55-3; Gases; Indium, 7440-74-6; Organometallic Compounds References: Barron, A.R., (1993) Chem. Soc. Rev., p. 93; Barron, A.R., (1993) Commun. Inorg. Chem., 14, p. 123; Barron, A.R., (1995) Macromol. Symp., 97, p. 15; Barron, A.R., (1995) Adv. Mater. Opt. Electron., 5, p. 245; Tolman, C.A., (1977) Chem. Rev., 77, p. 313; Landry, C.C., Harlan, C.J., Bott, S.G., Barron, A.R., (1995) Angew. Chem., Int. Ed. Engl., 34, p. 1201; McMahon, C.N., Bott, S.G., Barron, A.R., (1997) J. Chem. Soc., Dalton Trans., p. 3129; Francis, J.A., McMahon, C.N., Bott, S.G., Barron, A.R., (1999) Organometallics, 18, p. 4399; MacInnes, A.N., Power, M.B., Hepp, A.F., Barron, A.R., (1993) J. Organomet. Chem., 449, p. 95; Landry, C.C., Haynes, A., Barron, A.R., Haiduc, I., Silvestru, C., (1996) Polyhedron, 15, p. 391; Cleaver, W.M., Barron, A.R., McGuffrey, A.R., Bott, S.G., (1994) Polyhedron, 13, p. 2831; Gillan, E.G., Bott, S.G., Barron, A.R., (1997) Chem. Mater., 9, p. 796; Fletcher, D.A., McMeeking, R.F., Parkin, D., Chemical Database Service at Daresbury Laboratory (1996) J. Chem. Inf. Comput. Sci., 36, p. 746; Woski, M., Mitzel, N.W., (2004) Z. Naturforsch., B: Chem. Sci., 59, p. 269; Cowley, A.R., Downs, A.J., Marchant, S., MacRae, V.A., Taylor, R.A., Parsons, S., (2005) Organometallics, 24, p. 5702; Kuczkowski, A., Schulz, S., Nieger, M., (2004) Appl. Organomet. Chem., 18, p. 244; Uhl, W., Emden, C.H., Geiseler, G., Harms, K., (2003) Z. Anorg. Allg. Chem., 629, p. 2157; Uhl, W., (1989) Z. Anorg. Allg. Chem., 570, p. 37; Lehmkuhl, H., Olbrysch, O., Nehl, H., (1973) Liebigs Ann. Chem., p. 708; Lehmkuhl, H., Olbrysch, O., (1973) Liebigs Ann. Chem., p. 715; Kovar, R.A., Derr, H., Brandau, D., Callaway, J.O., (1975) Inorg. Chem., 14, p. 2809; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; 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 In, R., (1992) International Tables for Crystallography, Ed., , http://www.nsccs.ac.uk, A. J. C. Wilson, Kluwer Academic Publishers, Dordrecht, The Netherlands, p. 245 EPSRC National Service for Computational Chemistry Software. URL; 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.01, , 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; 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; Huzinaga, S., Klobukowski, M., (1988) THEOCHEM, 167, p. 1; Sipachev, V.A., (1985) THEOCHEM, 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; Hegarty, D., Robb, M.A., (1979) Mol. Phys., 38, p. 1795; Eade, R.H.E., Robb, M.A., (1981) Chem. Phys. Lett., 83, p. 362; Schlegel, H.B., Robb, M.A., (1982) Chem. Phys. Lett., 93, p. 43; Bernardi, F., Bottini, A., McDougall, J.J.W., Robb, M.A., Schlegel, H.B., (1984) Far. Symp. Chem. Soc., 19, p. 137; Yamamoto, N., Vreven, T., Robb, M.A., Frisch, M.J., Schlegel, H.B., (1996) Chem. Phys. Lett., 250, p. 373; Frisch, M.J., Ragazos, I.N., Robb, M.A., Schlegel, H.B., (1992) Chem. Phys. Lett., 189, p. 524; Stratmann, R.E., Scuseria, G.E., Frisch, M.J., (1998) J. Chem. Phys., 109, p. 8218; Bauernschmitt, R., Ahlrichs, R., (1996) Chem. Phys. Lett., 256, p. 454; Casida, M.E., Jamorski, C., Casida, K.C., Salahub, D.R., (1998) J. Chem. Phys., 108, p. 4439; 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; Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys., 82, p. 270; Wadt, W.R., Hay, P.J., (1985) J. Chem. Phys., 82, p. 284; Hay, P.J., Wadt, W.R., (1985) J. Chem. Phys., 82, p. 299; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans., p. 3650; Almenningen, A., Halvorsen, S., Haaland, A., (1971) Acta Chem. Scand., 25, p. 1937; Beagley, B., Schmidling, D.G., Steer, I.A., (1974) J. Mol. Struct., 21, p. 437; Rahman, A.F.M.M., Siddiqul, K.F., Oliver, J.P., (1982) Organometallics, 1, p. 881; Pauling, L., Laubengayer, A.W., (1941) J. Am. Chem. Soc., 63, p. 480; Barbe, G., Hencher, J.L., Shen, Q., Tuck, D.G., (1974) Can. J. Chem., 52, p. 3936; Jerius, J.J., Hahn, J.M., Rahman, A.F.M.M., Mols, O., Ilsey, W.H., Oliver, J.P., (1986) Organometallics, 5, p. 1812; Beachley Jr. O., T., Churchill, M.R., Pazik, J.C., Ziller, J.W., (1986) Organometallics, 5, p. 1817; Malone, J.F., McDonald, W.S., (1970) J. Chem. Soc. A, p. 3363; Harlan, C.J., Bott, S.G., Barron, A.R., (1995) J. Am. Chem. Soc., 117, p. 6465; McMahon, C.N., Barron, A.R., (1997) J. Chem. Crystallogr., 27, p. 171; Aitken, C.L., Barron, A.R., (1999) J. Chem. Crystallogr., 29, p. 993; Keys, A., Barbarich, T., Bott, S.G., Barron, A.R., (2000) J. Chem. Soc., Dalton Trans., p. 577; Bradley, D.C., Frigo, D.M., Hursthouse, M.B., Hussain, B., (1988) Organometallics, 7, p. 1112; Cleaver Phd Thesis, W.M., (1994), Harvard UniversityLeman, J.T., Barron, A.R., (1989) Organometallics, 8, p. 2214; Carty, A.J., Gynane, M.J., Lappert, M.F., Miles, S.J., Singh, A., Taylor, N.J., (1980) Inorg. Chem., 19, p. 3637; Brookhart, M., Green, M.L.H., (1983) J. Organomet. Chem., 250, p. 395; McDaniel, A.H., Allendorf, M.D., (2000) Chem. Mater., 12, p. 450; Allendorf, M.D., Melius, C.F., Bauschlicher, C.W., (1999) J. Phys. IV, 9, p. 8. , -23; Russell, D.K., (1996) Chem. Vap. Deposition, 2, p. 223; Jacko, M.G., Price, S.J.W., (1964) Can. J. Chem., 42, p. 1198; Clark, W.D., Price, S.J.W., (1968) Can. J. Chem., 46, p. 1633; Zhang, Y., Beuermann, T., Stuke, M., (1989) Appl. Phys. B, 48, p. 97; Zhang, Y., Stuke, M., (1988) Chemtronics, 3, p. 230; Cleaver, W.M., Barron, A.R., Zhang, Y., Stuke, M., (1992) Appl. Surf. Sci., 54, p. 8; Zhang, Y., Cleaver, W.M., Stuke, M., Barron, A.R., (1992) Appl. Phys. A, 55, p. 261",

year = "2008",

doi = "10.1039/b714168h",

language = "Undefined/Unknown",

pages = "404--410",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "The Royal Society of Chemistry",

number = "3",

}

Keys, A, Brain, PT, Morrison, CA, Callender, RL, Smart, BA, Wann, DA, Robertson, HE, Rankin, DWH & Barron, AR 2008, 'Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation', Dalton Transactions, no. 3, pp. 404-410. https://doi.org/10.1039/b714168h

Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation. / Keys, A.; Brain, P.T.; Morrison, C.A. et al.
In: Dalton Transactions, No. 3, 2008, p. 404-410.

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

TY - JOUR

T1 - Molecular structures of M(But)3 (M = Al, Ga, In) using gas-phase electron diffraction and ab initio calculations: Experimental and computational evidence for charge-transfer processes leading to photodissociation

AU - Keys, A.

AU - Brain, P.T.

AU - Morrison, C.A.

AU - Callender, R.L.

AU - Smart, B.A.

AU - Wann, D.A.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

AU - Barron, A.R.

N1 - Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus doi: 10.1039/b714168h PubMed ID: 18411850 Language of Original Document: English Correspondence Address: Rankin, D.W.H.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: [email protected] Chemicals/CAS: aluminum, 7429-90-5; butane, 106-97-8; gallium, 7440-55-3; indium, 7440-74-6; Aluminum, 7429-90-5; Butanes; Gallium, 7440-55-3; Gases; Indium, 7440-74-6; Organometallic Compounds References: Barron, A.R., (1993) Chem. Soc. Rev., p. 93; Barron, A.R., (1993) Commun. Inorg. Chem., 14, p. 123; Barron, A.R., (1995) Macromol. Symp., 97, p. 15; Barron, A.R., (1995) Adv. Mater. Opt. Electron., 5, p. 245; Tolman, C.A., (1977) Chem. Rev., 77, p. 313; Landry, C.C., Harlan, C.J., Bott, S.G., Barron, A.R., (1995) Angew. Chem., Int. Ed. Engl., 34, p. 1201; McMahon, C.N., Bott, S.G., Barron, A.R., (1997) J. Chem. 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PY - 2008

Y1 - 2008

N2 - The gas-phase structures of Al(But)3 and Ga(Bu t)3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (rh1) include rAl-C = 2.008(2) and rGa-C = 2.032(2). For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(But)3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(But)3 with those of Al(But)3 and Ga(But)3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two. This journal is © The Royal Society of Chemistry.

AB - The gas-phase structures of Al(But)3 and Ga(Bu t)3 have been investigated by electron diffraction and are shown to consist of monomeric units with very slightly pyramidal geometries. Salient structural parameters (rh1) include rAl-C = 2.008(2) and rGa-C = 2.032(2). For both compounds the ligand orientations and geometries are controlled by interligand interactions. The structures of M(But)3 (M = Al, Ga, In) have been calculated ab initio and those for the aluminium and gallium derivatives are in good agreement with the electron-diffraction structures. Comparison of the ab initio calculated structure of In(But)3 with those of Al(But)3 and Ga(But)3 suggests that the significantly different photochemistry exhibited by the former does not result from structural factors. In fact the compounds undergo a charge-transfer process in the UV region, with the wavelength required calculated to be slightly longer for the indium compound than for the other two. This journal is © The Royal Society of Chemistry.

KW - Aluminum compounds

KW - Charge transfer

KW - Electron diffraction

KW - Gallium compounds

KW - Ligands

KW - Molecular interactions

KW - Photodissociation

KW - Interligand interactions

KW - Ligand orientations

KW - Monomeric units

KW - Molecular structure

KW - aluminum

KW - butane

KW - gallium

KW - indium

KW - organometallic compound

KW - article

KW - chemical model

KW - chemical structure

KW - chemistry

KW - computer simulation

KW - electron

KW - gas

KW - phase transition

KW - photochemistry

KW - quantum theory

KW - X ray crystallography

KW - Aluminum

KW - Butanes

KW - Computer Simulation

KW - Crystallography, X-Ray

KW - Electrons

KW - Gallium

KW - Gases

KW - Indium

KW - Models, Chemical

KW - Models, Molecular

KW - Organometallic Compounds

KW - Phase Transition

KW - Photochemistry

KW - Quantum Theory

U2 - 10.1039/b714168h

DO - 10.1039/b714168h

M3 - Article

SN - 1477-9226

SP - 404

EP - 410

JO - Dalton Transactions

JF - Dalton Transactions

IS - 3

ER -