Molecular structures of the digermanes Me2XGeGeXMe2 (X = Me, Cl, and H): an ab initio study combined with experimental investigation by raman spectroscopy and gas electron diffraction

TY - JOUR

T1 - Molecular structures of the digermanes Me2XGeGeXMe2 (X = Me, Cl, and H)

T2 - an ab initio study combined with experimental investigation by raman spectroscopy and gas electron diffraction

AU - Hölbling, M.

AU - Masters, S.L.

AU - Flock, M.

AU - Baumgartner, J.

AU - Hassler, K.

AU - Robertson, H.E.

AU - Wann, D.A.

N1 - Cited By (since 1996):3 Export Date: 1 October 2013 Source: Scopus CODEN: INOCA doi: 10.1021/ic7018764 Language of Original Document: English Correspondence Address: Masters, S. L.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected] References: Eliel, E.L., Wilen, S.H., (1994) Stereochemistry of Organic Compounds, , For instance, see:, Wiley: New York; Beagley, B., Conrad, A.R., Freeman, J.M., Monaghan, J.J., Norton, B.G., Holywell, G.C., (1972) J. Mol. Struct, 11, pp. 371-380; Schleyer, P.V.R., Kaupp, M., Hampel, F., Bremer, M., Mislow, K., (1992) J. Am. Chem. Soc, 114, pp. 6791-6797; Aksnes, D.W., Kimtys, L., (1995) Acta Chem. Scand, 49 (10), pp. 722-727; Mohamed, T.A., (2003) J. Mol. Struct. (THEOCHEM), 635, pp. 161-172; Jähn, A., Schenzel, K., Zink, R., Hassler, K., (1999) Spectrochim. Acta Part A, 55, p. 2677; Kveseth, K., (1979) Acta Chem. Scand, A33 (6), pp. 453-462; Hnyk, D., Fender, R.S., Robertson, H.E., Rankin, D.W.H., Brühl, M., Hassler, K., Schenzel, K., (1995) J. Mol. Struct, 346, pp. 215-229; Hinchley, S.L., Robertson, H.E., Parkin, A., Rankin, D.W.H., Tekautz, G., Hassler, K., (2004) Dalton Trans, 759, p. 766; Hinchley, S.L., Smart, B.A., Morrison, C.A., Robertson, H.E., Rankin, D.W.H., Coxall, R.A., Parsons, S., Mawhorter, R.J., (2001) J. Chem. Soc., Dalton Trans, 19, pp. 2916-2925; Song, L., Lin, Y., Wu, W., Zhang, Q., Mo, Y., (2005) J. Phys. Chem. A, 109, pp. 2310-2316; Goodman, L., Pophoristic, V., Wang, W., (2002) Int. J. Quantum Chem, 90, pp. 657-662; Urban, J., Schreiner, P.R., Vacek, G., Schleyer, P.V.R., Huang, J.Q., Leszczynski, J., (1997) Chem. Phys. Lett, 264, pp. 441-448; Oberhammer, H., Sundermeyer, W., (1994) J. Mol. Struct, 323, pp. 125-128; Hölbling, M., Lobreyer, T., Flock, M., Baumgartner, J., Hassler, K., (2007) Eur. J. Inorg. Chem, pp. 4952-4957; Triplett, K., Curtis, M.D., (1976) J. Organomet. Chem, 107, pp. 23-32; Zink, R.P.D., Graz, U., Graz, A., (1997)(1997) SAINTPLUS: Software Reference Manual, , version 6.45; Bruker-AXS: Madison, WI; Blessing, R.H., (1995) Acta Crystallogr. A, 51, pp. 33-38; SADABS, version 2.1; Bruker AXS: Madison, WI, 1998Sheldrick, G. M. SHELX97, Programs for Crystal Structure Analysis, release 97-2; Universität Göttingen: Göttingen, Germany, 1998Frisch, M. J, Tracks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, KeitSipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 22, pp. 143-151; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans, 6, pp. 954-957; 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, 19, pp. 3221-3228; 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, 16, pp. 2469-2476; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, 100, p. 245. , Wilson, A. J. C, Ed, Kluwer Academic Publishers: Dordrecht, The Netherlands; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H.J., (1996) Chem. Soc., Dalton Trans, 24, pp. 4589-4596; 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, pp. 12280-12287; Mitzel, N.W., Rankin, D.W.H., (1996) Dalton Trans, 24, pp. 3650-3662; Draeger, M., Ross, L., (1981) Z. Anorg. Allg. Chem, 476, pp. 95-104; Draeger, M., Ross, L., (1980) Z. Anorg. Allg. Chem, 460, pp. 207-216; Parkanyi, L., Kalman, A., Sharma, S., Nolen, D.M., Pannell, K.H., (1994) Inorg. Chem, 33 (1), pp. 180-182; Weidenbruch, M., Grimm, F.-T., Herrndorf, M., Schaefer, A., Peters, K., von Schnering, H.G., (1988) J. Organomet. Chem, 341, pp. 335-343; Griffiths, J.E., Walrafen, G.E., (1964) J. Chem. Phys, 40, pp. 321-328; Swick, D.A., Karle, I.L., (1955) J. Chem. Phys, 23, pp. 1499-1504; Morino, Y., Hirota, E., (1958) J. Chem. Phys, 28, pp. 185-197; Adams, S., Draeger, M., Mathiasch, B., (1986) Z. Anorg. Allg. Chem, 532, pp. 81-89; Buschmann, J., Lentz, D., Luger, P., Rottger, M., (2000) Acta Crystallogr., Sect.C: Cryst.Struct. Commun, 56, pp. 121-122; Lefferts, J.L., Molloy, K.C., Hossain, M.B., van der Helm, D., Zuckerman, J.J., (1982) J. Organomet. Chem, 240 (4), pp. 349-361; Blake, A.J., Cradock, S., Ebsworth, E.A.V., Franklin, K.C., (1990) Angew. Chem, 102 (1), pp. 87-89; Schlemper, E.O., Britton, D., (1966) Inorg. Chem, 5, pp. 511-514

PY - 2008/4/21

Y1 - 2008/4/21

N2 - Ab initio calculations were carried out to investigate the potential-energy surface for internal rotation of the methylated digermanes hexamethyldigermane Me3GeGeMe3 (1), dichlorotetramethyldigermane Me 2ClGeGeClMe2 (2), and tetramethyldigermane Me 2HGeGeHMe2 (3). Different basis sets [6-31+G(d), SDD, aug-cc-pVTZ] were employed at the DFT and MP2 levels of theory to optimize structures and to calculate energies and vibrational frequencies. For 1, one minimum representing a staggered structure was located on the potential-energy surface. For 2 and 3, antiperiplanar conformations with C2 symmetry were found to be the global minima. Additionally, synclinal minima were located for 2 and 3 when certain basis sets were employed. Determination of structural parameters in the gas phase by gas electron diffraction confirmed the computed predictions for all three compounds. For 2 and 3, the ratios of antiperiplanar to synclinal conformer were detected to be 90:10 (328 K) and 72:28 (293 K), respectively, by gas electron diffraction. The experimentally determined GeGe bond lengths in 1, 2, and 3 in the gas phase are 241.4(1), 242.7(2) (averaged for antiperiplanar and synclinal), and 241.7(1) pm (equal for antiperiplanar and synclinal). Only averaged structures were observed, using Raman spectroscopy, for 2 and 3 because the wavenumber differences are small between conformers and there is only a small contribution from the second conformer in each case. For 2, the crystal structure was also determined by X-ray diffraction. An anticlinal structure (with Cl atoms eclipsing the C atoms) was found with a GeGe bond length of 242.1 pm. © 2008 American Chemical Society.

AB - Ab initio calculations were carried out to investigate the potential-energy surface for internal rotation of the methylated digermanes hexamethyldigermane Me3GeGeMe3 (1), dichlorotetramethyldigermane Me 2ClGeGeClMe2 (2), and tetramethyldigermane Me 2HGeGeHMe2 (3). Different basis sets [6-31+G(d), SDD, aug-cc-pVTZ] were employed at the DFT and MP2 levels of theory to optimize structures and to calculate energies and vibrational frequencies. For 1, one minimum representing a staggered structure was located on the potential-energy surface. For 2 and 3, antiperiplanar conformations with C2 symmetry were found to be the global minima. Additionally, synclinal minima were located for 2 and 3 when certain basis sets were employed. Determination of structural parameters in the gas phase by gas electron diffraction confirmed the computed predictions for all three compounds. For 2 and 3, the ratios of antiperiplanar to synclinal conformer were detected to be 90:10 (328 K) and 72:28 (293 K), respectively, by gas electron diffraction. The experimentally determined GeGe bond lengths in 1, 2, and 3 in the gas phase are 241.4(1), 242.7(2) (averaged for antiperiplanar and synclinal), and 241.7(1) pm (equal for antiperiplanar and synclinal). Only averaged structures were observed, using Raman spectroscopy, for 2 and 3 because the wavenumber differences are small between conformers and there is only a small contribution from the second conformer in each case. For 2, the crystal structure was also determined by X-ray diffraction. An anticlinal structure (with Cl atoms eclipsing the C atoms) was found with a GeGe bond length of 242.1 pm. © 2008 American Chemical Society.

U2 - 10.1021/ic7018764

DO - 10.1021/ic7018764

M3 - Article

SN - 0020-1669

VL - 47

SP - 3023

EP - 3033

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -