C2-Symmetric ansa-lanthanidocene complexes. Synthesis via silylamine elimination and β-SiH agostic rigidity

Journal of the American Chemical Society

Volumn 122, Issue 13, 2000, Pages 3080-3096

  Eppinger, Jörg ^a   Spiegler, Michael ^a   Hieringer, Wolfgang ^a   Herrmann, Wolfgang A ^a   Anwander, Reiner ^a  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; FLUORENE DERIVATIVE; INDENE DERIVATIVE; LANTHANIDE; LANTHANUM; LUTETIUM; NEODYMIUM; SCANDIUM; SILANE DERIVATIVE;

ARTICLE; CHEMICAL BINDING; CHEMICAL STRUCTURE; COMPLEX FORMATION; INFRARED SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; RACEMIC MIXTURE; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS; THERMODYNAMICS; X RAY CRYSTALLOGRAPHY;

EID: 0034607379     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992786a     Document Type: Article

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73. 34 point out that the ring current only partly contributes to the high upfield shift of the SiH proton.
74. H,H coupling via Y.
75. -1.
76. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
77. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
78. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
79. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
80. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
81. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
82. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
83. 2-SiH). (a) 136 Hz for M = Cr: Driess, M.; Reigys, M.; Pritzkow, H. Angew. Chem. 1992, 104, 1514-1516; Angew. Chem., Int. Ed. Engl. 1992, 31, 1510-1512. (b) 92 Hz for M = Ti: Ohff, A.; Kosse, P.; Baumann, W.; Tillack, A.; Kempe, R.; Görls, H.; Burlakov, V. V.; Rosenthal, U. J. Am. Chem. Soc. 1995, 117, 10399-10400. (c) 20-70 Hz for M = Mo: Luo, X.-L.; Kubas, G. J.; Bryan, J. C.; Burns, J. C.; Unkefer, C. J. J. Am. Chem. Soc. 1994, 116, 10312-10313. (d) Crabtree, R. H.; Pritzkow, H. Angew. Chem. 1993, 105, 828-845; Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805. (e) Crabtree, R. H.; Hamilton, D. G. Adv. Organomet. Chem. 1988, 28, 299-358. (f) Schubert, H. Adv. Organomet. Chem. 1990, 30, 151-187.
84. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
85. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
86. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
87. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
88. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
89. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
90. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
91. σ-Bond metathesis reactions involving Ln-C/Si-H transpositions were reported to occur in hydrosilylation reactions: (a) Sakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351. (c) Onozawa, S.; Sakakura, T.; Tanaka, M. Tetrahedron Lett. 1994, 35, 8177-8180. (d) Ziegler, T.; Folga, E. J. Organomet. Chem. 1994, 478, 57-65. (e) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416. (f) Radu, N. S.; Tilley, T. D. J. Am. Chem. Soc. 1995, 117, 5863-5864. (g) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (h) Voskoboynikov, A. Z.; Parshina, I. N.; Shestakova, A. K.; Butin, K. P.; Beletskaya, I. P.; Kuz'mina, L. G.; Howard, J. A. K. Organometallics 1997, 16, 4041-4055.
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100. In theoretical studies the asymmetric geometry has been attributed to an interaction between the electron-deficient Ln(III) center and the electron density of the Si-C bond: (a) Tatsumi, K.; Nakamura, A. J. Am. Chem. Soc. 1987, 109, 3195-3206. (b) Bursten, B. E ; Fang, A. Inorg. Chim. Acta 1985, 110, 153-160.
101. Correspondingly, the interactions discussed in this paper involve the electron density of the SiH fragment: Scherer, W. Ph.D. Thesis, Technische Universität München, 1993
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104. All SiH hydrogens atoms were located in difference Fourier maps and successfully refined. Of course, the usual caution regarding the accuracy of hydrogen positions in heavy atom structures was applied. In fact, though a lengthening of the agostically interacting Si-H bonds should be expected, the refined SiH positions yield bond lengths of 1.43-1.47 Å, which are even shorter than normal SiH distances in hydrosilanes (1.47-1.50 Å; Lukevics, E.; Pudowa, O., Sturkovich, R. Molecular Structure of Organosilicon Compounds; Ellis-Horwood: Chichester, U.K., 1989).
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113. The more covalent dimethylsilyl-bridged ferrocenyl complexes exhibit tilt angles β as large as 40.0°, affording a nearly planar arrangement of both cyclopentadienyl rings: (a) Rulhuns, R.; Lough, A. J.; Mannus, I. Angew. Chem. 1996, 108, 1929-1931; Angew. Chem., Int. Ed. Engl. 1996, 35, 1805-1807. (b) Herberhold, M.; Steffi, U.; Milius, W.; Wrackmeyer, B. Angew. Chem. 1996, 108, 1927-1929; Angew. Chem., Int. Ed. Engl. 1996, 35, 1863-1864. (c) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. Helv. Chim. Acta 1976, 59, 2402-2406.
114. The more covalent dimethylsilyl-bridged ferrocenyl complexes exhibit tilt angles β as large as 40.0°, affording a nearly planar arrangement of both cyclopentadienyl rings: (a) Rulhuns, R.; Lough, A. J.; Mannus, I. Angew. Chem. 1996, 108, 1929-1931; Angew. Chem., Int. Ed. Engl. 1996, 35, 1805-1807. (b) Herberhold, M.; Steffi, U.; Milius, W.; Wrackmeyer, B. Angew. Chem. 1996, 108, 1927-1929; Angew. Chem., Int. Ed. Engl. 1996, 35, 1863-1864. (c) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. Helv. Chim. Acta 1976, 59, 2402-2406.
115. The more covalent dimethylsilyl-bridged ferrocenyl complexes exhibit tilt angles β as large as 40.0°, affording a nearly planar arrangement of both cyclopentadienyl rings: (a) Rulhuns, R.; Lough, A. J.; Mannus, I. Angew. Chem. 1996, 108, 1929-1931; Angew. Chem., Int. Ed. Engl. 1996, 35, 1805-1807. (b) Herberhold, M.; Steffi, U.; Milius, W.; Wrackmeyer, B. Angew. Chem. 1996, 108, 1927-1929; Angew. Chem., Int. Ed. Engl. 1996, 35, 1863-1864. (c) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. Helv. Chim. Acta 1976, 59, 2402-2406.
116. The more covalent dimethylsilyl-bridged ferrocenyl complexes exhibit tilt angles β as large as 40.0°, affording a nearly planar arrangement of both cyclopentadienyl rings: (a) Rulhuns, R.; Lough, A. J.; Mannus, I. Angew. Chem. 1996, 108, 1929-1931; Angew. Chem., Int. Ed. Engl. 1996, 35, 1805-1807. (b) Herberhold, M.; Steffi, U.; Milius, W.; Wrackmeyer, B. Angew. Chem. 1996, 108, 1927-1929; Angew. Chem., Int. Ed. Engl. 1996, 35, 1863-1864. (c) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. Helv. Chim. Acta 1976, 59, 2402-2406.
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120. Shannon, R. D. Acta Crystallogr. 1976, A32, 751-767.
121. Klooster, W. T.; Brammer, L.; Schaverien, C. J.; Budzelaar, P. H. M. J. Am. Chem. Soc. 1999, 121, 1381-1382.
122. (a) Klooster, W. T.; Lu, R. S.; Anwander, R.; Evans, W. J.; Koetzle, T. F.; Bau, R. Angew. Chem. 1998, 110, 1326-1329; Angew. Chem., Int. Ed. Engl. 1998, 37, 1268-1270.
123. (a) Klooster, W. T.; Lu, R. S.; Anwander, R.; Evans, W. J.; Koetzle, T. F.; Bau, R. Angew. Chem. 1998, 110, 1326-1329; Angew. Chem., Int. Ed. Engl. 1998, 37, 1268-1270.
124. (b) Evans, B. J.; Anwander, R.; Ziller, J. W.; Khan, S. I. Inorg. Chem. 1995, 34, 5927-5930.
125. aromat-H = 1.090 Å; ZH-C-Si = 107°. The hydrogen atoms of the aromatic systems were placed on the bisector of the C-CH-C angles.
126. (a) The correlation between the Si-N-Si angles and the pertinent Si-N distances was based on 72 data points, taken from 17 compounds (data sources: CSD, refs 15, 16 and this publication).
127. n hybrid and the Si-N distance d (d = S(0) + kP), from cos a = (P - 1)/P (α = Si-N-Si angle) the correlation function d = S(0) + k/(1 - cos α) can be obtained. This function was fitted to the data points by least-squares refinement. The resulting parameters are, for the metallocene silylamides, S(0) = 1.440 and k = 0.425 (rms = 0.0132) and, for unperturbated monoagostic silylamides, S(0) = 1.300, k = 0.881 (rms = 0.0154). For 180° > α > 90°, theoretical Si-N bond distances in the range 1.653 < d < 1.866 Å and 1.530 < d < 2.179 Å can be derived for metallocene silylamide complexes and for unperturbated silylamide complexes, respectively.
128. + cations, and hence insignificantly increased Si-C-Si angles.
129. + cations, and hence insignificantly increased Si-C-Si angles.
130. For polyagostic Ln⋯Me interactions, see: Tilley, T. D.; Andersen, R. A.; Zalkin, A. Inorg. Chem. 1984, 23, 2271-2276.
131. Herrmann, W. A.; Munck, F. C.; Artus, G. R. J.; Runte, O.; Anwander, R. Organometallics 1997, 16, 682-688.
132. So far, few C-H⋯N distances have been reported. A relatively strong C-H⋯N hydrogen bond in methylnitrile results in a close C⋯N contact of 318 pm: Dulmage, W. J.; Lipscomb, W. N. Acta Crystallogr. 1951, 4, 330-335. For a recent discussion, see: Mascal, M. Chem. Commun. 1998, 303-304.
133. So far, few C-H⋯N distances have been reported. A relatively strong C-H⋯N hydrogen bond in methylnitrile results in a close C⋯N contact of 318 pm: Dulmage, W. J.; Lipscomb, W. N. Acta Crystallogr. 1951, 4, 330-335. For a recent discussion, see: Mascal, M. Chem. Commun. 1998, 303-304.
134. (a) Fraser, R. R.; Besse, M.; Mansour, T. S. J. Chem. Soc., Chem. Commun. 1983, 620-621.
135. (b) Fraser, R. R.; Mansour, T. S.; Savard, S. J. Org. Chem. 1985, 50, 3232-3234.
136. (c) Fraser, R. R.; Mansour, T. S.; Savard, S. Can. J. Chem. 1985, 63, 3505-3509 and references therein.
137. a value estimations, see: (a) Streitwieser, A., Jr.; Juaristi, E.; Nebenzahl L. L. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 323-382. (b) Reutov, O. A.; Beletskaya, I. P.; Butin, K. P. CH-Acids; Pergamon Press: Oxford, 1978. (c) For recent advances in measurement techniques, see: Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964. (d) Bordwell, F. G.; Cheng, P.-J.; Ji, G.-Z.; Satish, A. V.; Zhang, X. J. Am. Chem. Soc. 1991, 113, 9790-9795. (e) Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
138. a value estimations, see: (a) Streitwieser, A., Jr.; Juaristi, E.; Nebenzahl L. L. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 323-382. (b) Reutov, O. A.; Beletskaya, I. P.; Butin, K. P. CH-Acids; Pergamon Press: Oxford, 1978. (c) For recent advances in measurement techniques, see: Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964. (d) Bordwell, F. G.; Cheng, P.-J.; Ji, G.-Z.; Satish, A. V.; Zhang, X. J. Am. Chem. Soc. 1991, 113, 9790-9795. (e) Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
139. a value estimations, see: (a) Streitwieser, A., Jr.; Juaristi, E.; Nebenzahl L. L. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 323-382. (b) Reutov, O. A.; Beletskaya, I. P.; Butin, K. P. CH-Acids; Pergamon Press: Oxford, 1978. (c) For recent advances in measurement techniques, see: Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964. (d) Bordwell, F. G.; Cheng, P.-J.; Ji, G.-Z.; Satish, A. V.; Zhang, X. J. Am. Chem. Soc. 1991, 113, 9790-9795. (e) Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
140. a value estimations, see: (a) Streitwieser, A., Jr.; Juaristi, E.; Nebenzahl L. L. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 323-382. (b) Reutov, O. A.; Beletskaya, I. P.; Butin, K. P. CH-Acids; Pergamon Press: Oxford, 1978. (c) For recent advances in measurement techniques, see: Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964. (d) Bordwell, F. G.; Cheng, P.-J.; Ji, G.-Z.; Satish, A. V.; Zhang, X. J. Am. Chem. Soc. 1991, 113, 9790-9795. (e) Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
141. a value estimations, see: (a) Streitwieser, A., Jr.; Juaristi, E.; Nebenzahl L. L. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 323-382. (b) Reutov, O. A.; Beletskaya, I. P.; Butin, K. P. CH-Acids; Pergamon Press: Oxford, 1978. (c) For recent advances in measurement techniques, see: Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964. (d) Bordwell, F. G.; Cheng, P.-J.; Ji, G.-Z.; Satish, A. V.; Zhang, X. J. Am. Chem. Soc. 1991, 113, 9790-9795. (e) Streitwieser, A.; Ciula, J. C.; Krom, J. A.; Thiele, G. J. Org. Chem. 1991, 56, 1074-1076.
142. Matthews, W. A.; Bares, J. E.; Bartmess, J. E.; Bordwell, F. G.; Cornforth, F. J.; Drucker, G. E.; Magolin, Z.; McCallum, R. J.; Mc. Collum, G. J., Vanier, N. R. J. Am. Chem. Soc. 1975, 97, 7006-7014.
143. For discussions of ssip/cip equilibria, see refs 62a,b and the following: (a) O'Brien, D. H. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 271-322. (b) Eiermann, M.; Hafner, K. J. Am. Chem. Soc. 1992, 114, 135-140. (c) O'Brian, H. D.; Russel, R. C.; Hart, A. J. J. Am. Chem. Soc. 1979, 101, 633-639. (d) Grutzner, J. B.; Lawlor, J. M.; Jackman, L. M. J. Am. Chem. Soc. 1972, 64, 2306-2314.
144. For discussions of ssip/cip equilibria, see refs 62a,b and the following: (a) O'Brien, D. H. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 271-322. (b) Eiermann, M.; Hafner, K. J. Am. Chem. Soc. 1992, 114, 135-140. (c) O'Brian, H. D.; Russel, R. C.; Hart, A. J. J. Am. Chem. Soc. 1979, 101, 633-639. (d) Grutzner, J. B.; Lawlor, J. M.; Jackman, L. M. J. Am. Chem. Soc. 1972, 64, 2306-2314.
145. For discussions of ssip/cip equilibria, see refs 62a,b and the following: (a) O'Brien, D. H. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 271-322. (b) Eiermann, M.; Hafner, K. J. Am. Chem. Soc. 1992, 114, 135-140. (c) O'Brian, H. D.; Russel, R. C.; Hart, A. J. J. Am. Chem. Soc. 1979, 101, 633-639. (d) Grutzner, J. B.; Lawlor, J. M.; Jackman, L. M. J. Am. Chem. Soc. 1972, 64, 2306-2314.
146. For discussions of ssip/cip equilibria, see refs 62a,b and the following: (a) O'Brien, D. H. In Comprehensive carbanion chemistry, Part A; Buncel, E., Durst, T., Eds.; Elsevier-North Holland: Amsterdam, 1980; pp 271-322. (b) Eiermann, M.; Hafner, K. J. Am. Chem. Soc. 1992, 114, 135-140. (c) O'Brian, H. D.; Russel, R. C.; Hart, A. J. J. Am. Chem. Soc. 1979, 101, 633-639. (d) Grutzner, J. B.; Lawlor, J. M.; Jackman, L. M. J. Am. Chem. Soc. 1972, 64, 2306-2314.
147. Harder, S.; Lutz, M.; Straub, A. W. G. Organometallics 1997, 177, 107-113.
148. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
149. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
150. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
151. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
152. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
153. a value determinations, caused by 1,5-sigmatropic shifts of silyl groups, see: (e) Bordwell, F. G.; Satish, A. V. J. Am. Chem. Soc. 1992, 114, 10173-10176. (f) Zhang, S.; Zhang, X.-M.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
154. Interestingly, the silylated indenyl compounds 8b and 9b show the same diastereotopic signal pattern (two doublets) for the two silylmethyl groups as the ansa-metallocene amide complexes described above. The signals of the Si-H moieties are shaped differently, additionally emphasizing the Ln⋯HSi coupling in the rare earth metallocene complexes.
155. π interactions for silylamines have been discussed controversely, see: Ebsworth, E. A. V. Volatile Silicon Compounds; Pergamon Press: Oxford, 1963.
156. 2 with bis(dimethylsilyl)amine: Eppinger, J.; Herdtweck, E.; Anwander, R. Polyhedron 1998, 17, 1195-1201.
157. (a) Forsyth, C. M.; Nolan, S. P.; Marks, T. J. Organametallics 1991, 10, 2543-2545.
158. (b) Sakakura, T.; Lautenschlager, H.-J.; Nakajima, M.; Tanaka, M. Chem. Lett. 1991, 913-916.
159. Anwander R.; Görlitzer, H. W.; Gerstberger, G.; Eppinger, J., unpublished results.
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