Synthesis and structure of the germylyne complexes trans-[X (dppe)2W≡Ge(η1-Cp) ] (X = Cl, Br, I) and comparison of the W≡E bonds (E = C, Ge) by density functional calculations

Angewandte Chemie - International Edition

Volumn 39, Issue 15, 2000, Pages 2778-2781

  Filippou, Alexander C ^a   Philippopoulos, Athanassios I ^a   Portius, Peter ^a   Neumann, Dirk U ^a  

^a HUMBOLDT UNIVERSITY   (Germany)

Author keywords

Carbyne complexes; Density functional calculations; Germanium; Germylyne complexes; Multiple bonds

Indexed keywords

BROMINE; CHLORINE; IODINE; TOLUENE;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; SYNTHESIS; THERMOSTABILITY;

EID: 0034604665     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20000804)39:15<2778::AID-ANIE2778>3.0.CO;2-2     Document Type: Article

References (29)

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2. b) R. R. Schrock, Acc. Chem. Res. 1986, 19, 342;
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4. H. Fischer, P. Hofmann, F. R. Kreißl, R. R. Schrock, K. Weiss, Carbyne Complexes, VCH, Weinheim, 1988;
5. e) F. G. A. Stone, Adv. Organomet. Chem. 1990, 31, 53;
6. f) A. Mayr, H. Hoffmeister, Adv. Organomet. Chem. 1992, 32, 227.
7. 2), has been described: S. D. Grumbine, R. K. Chadha, T. D. Tilley, J. Am. Chem. Soc. 1992, 114, 1518.
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9. b) L. Pu, B. Twamley, S. T. Haubrich, M. M. Olmstead, B. V. Mork, R. S. Simons, P. P. Power, J. Am. Chem. Soc. 2000, 122, 650, and references therein.
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11. b) J. Chatt, R. L. Richards, J. Organomet. Chem. 1982, 239, 65;
12. R. L. Richards, Chem. Br. 1988, 24, 133.
13. Ebullioscopic measurements show that the complexes 2a-c are monomeric in solution. In the solid state 2a is monomeric, whereas 2b is a Br-bridged dimer and 2c forms a ladderlike coordination polymer linked by I bridges: J. G. Winter, P. Portius, G. Kociok-Köhn, R. Steck, A. C. Filippou, Organometallics 1998, 17, 4176.
14. -3, Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-142852. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (H 44)1223-336-033; e-mail: deposit@ccdc.cam. ac.uk).
15. a) A. C. Filippou, J. G. Winter, G. Kociok-Köhn, I. Hinz, J. Chem. Soc. Dalton Trans. 1998, 2029;
16. b) A. C. Filippou, J. G. Winter, G. Kociok-Köhn, C. Troll, I. Hinz, Organometallics 1999, 18, 2649.
17. R. Steck, thesis, Humboldt-Universität, Berlin, 1998.
18. a) N. Trong Anh, M. Elian, R. Hoffmann, J. Am. Chem. Soc. 1978, 100, 110;
19. b) P. Jutzi, Chem. Rev. 1986, 86, 983, and references therein.
20. 4W=EMe] and 4a-7a.
21. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
22. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
23. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
24. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
25. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
26. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
27. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
28. The gradient corrected functionals BP86 were used (A.D. Becke, Phys. Rev. A 1988, 38, 3098; J. P. Perdew, Phys. Rev. B 1986, 33, 8822). For the W atom and the elements Ge, Cl, and P the pseudo potentials (W: P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299; Ge, Cl, P; G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 1988, 65, 1321) and corresponding valence basis sets were used (W: 441/2111/21 and 441/ 2111/111/1; Ge, Cl, P: 31/31/1 and 211/211/11). Together with the standard basis sets 6-31G(d) (P.C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213) and 6-311G(2d,p) (R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650) for the remaining elements the combinations II and III were obtained (Table I). The calculations were performed with Gaussian 98 (Gaussian98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Slefanov, G. Lui, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998) and CDA 2.1 (charge decomposition analysis; S. Dapprich, G, Frenking, CDA 2.1, Marburg, 1994).
29. P. Jutzi, J. Organomet. Chem. 1990, 400, 1.