Rare-Earth-Metal Amido Complexes: Catalysts
4796 4810
120, 4871 4872; k) A. T. Gilbert, B. L. Davis, T. J. Emge, R. D.
Broene, Organometallics 1999, 18, 2125 2132; l) V. M. Arredondo, S.
Tian, F. E. McDonald, T. J. Marks, J. Am. Chem. Soc. 1999, 121, 3633
3639; m) G. A. Molander, E. D. Dowdy, J. Org. Chem. 1999, 64, 6515
6517; n) V. M. Arredondo, F. E. McDonald, T. J. Marks, Organo-
metallics 1999, 18, 1949 1960; o) G. A. Molander, E. D. Dowdy, S. K.
Pack, J. Org. Chem. 2001, 66, 4344 4347; p) J.-S. Ryu, T. J. Marks,
F. E. McDonald, Org. Lett. 2001, 3, 3091 3094.
63, 1364 1365; e) K. B. Simonsen, K. V. Gothelf, K. A. J˘rgensen, J.
Org. Chem. 1998, 63, 7536 7538; f) P. Kratky, U. Haslinger, M.
Widhalm, Monatsh. Chem. 1998, 129, 1319 1327.
[21] P. L. Arnold, L. S. Natrajan, J. J. Hall, S. J. Bird, C. Wilson, J.
Organomet. Chem. 2002, 647, 205 215.
[22] a) T. J. Boyle, D. L. Barnes, J. A. Heppert, L. Morales, F. Takusagawa,
J. W. Connolly, Organometallics 1992, 11, 1112 1126; b) T. J. Boyle,
N. W. Eilerts, J. A. Heppert, F. Takusagawa, Organometallics 1994, 13,
2218 2229; c) E. J. Corey, M. A. Letavic, M. C. Noe, S. Sarshar,
Tedrahedron Lett. 1994, 35, 7553 7556; d) T. Arai, H. Sasai, K.
Yamaguchi, M. Shibasaki, J. Am. Chem. Soc. 1998, 120, 441 442;
e) M. Terada, Y. Matsumoto, Y. Nakamura, K. Mikami, Inorg. Chim.
Acta 1999, 296, 267 272; f) T. Davis, J. Balsells, P. J. Carroll, P. J.
Walsh, Org. Lett. 2001, 3, 699 702; g) H. Nˆth, A. Schlegel, M. Suter,
J. Organomet. Chem. 2001, 621, 231 241; h) S. Chitsaz, B. Neum¸ller,
Organometallics 2001, 20, 2338 2343; i) A. Kayal, S. C. Lee, Inorg.
Chem. 2001, 41, 321 330.
[23] a) A. Kayal, A. F. Ducruet, S. C. Lee, Inorg. Chem. 2000, 40, 3696
3704; b) H. C. Aspinall, J. M. Bickley, J. L. M. Dwyer, N. Greeves, A.
Steiner, Angew. Chem. 2000, 112, 2980 2983; Angew. Chem. Int. Ed.
2000, 39, 2858 2861.
[24] a) W. J. Evans, J. M. Olofson, J. W. Ziller, Inorg. Chem. 1989, 28,
4308 4309, references therein; b) M. H. Chisholm, Polyhedron 1983,
2, 681 721; c) R. C. Mehrotra, A. Singh, U. M. Tripathi, Chem. Rev.
1991, 91, 1287 1303; d) R. Anwander, Top. Curr. Chem. 1996, 179,
149 245.
[6] a) M. R. B¸rgstein, H. Berberich, P. W. Roesky, Organometallics 1998,
17, 1452 1454; b) Y. K. Kim, T. Livinghouse, J. E. Bercaw, Tedrahe-
dron Lett. 2001, 42, 2933 2935; c) Y. K. Kim, T. Livinghouse, Angew.
Chem. 2002, 114, 3797 3799; Angew. Chem. Int. Ed. 2002, 41, 3645
3647.
[7] For an overview of applications of rare earth metals as reagents or
catalysts in organic synthesis and polymerization catalysis see:
a) G. A. Molander, Chem. Rev. 1992, 92, 29 68; b) G. A. Molander,
C. R. Harris, Chem. Rev. 1996, 96, 307 338; c) F. T. Edelmann, Top.
Curr. Chem. 1996, 179, 247 276; d) H. Yasuda, Top. Organomet.
Chem. 1999, 2, 255 283; e) H. C. Aspinall, Chem. Rev. 2002, 102,
1807 1850; f) G. A. Molander, J. A. C. Romero, Chem. Rev. 2002,
102, 2161 2185; g) M. Shibasaki, N. Yoshikawa, Chem. Rev. 2002,
102, 2187 2210; h) S. Kobayashi, M. Sugiura, H. Kitagawa, W. W.-L.
Lam, Chem. Rev. 2002, 102, 2227 2302; i) K. Mikami, M. Terada, H.
Matsuzawa, Angew. Chem. 2002, 114, 3704 3722; Angew. Chem. Int.
Ed. 2002, 41, 3554 3571; j) Z. Hou, Y. Wakatsuki, Coord. Chem. Rev.
2002, 231, 1 22.
[8] Epimerization of planar chiral cyclopentadienyl complexes is quite a
general phenomenon in rare-earth-metal chemistry, see: a) M. A.
Giardello, V. P. Conticello, L. Brard, M. Sabat, A. L. Rheingold, C. L.
Stern, T. J. Marks, J. Am. Chem. Soc. 1994, 116, 10212 10240;
b) C. M. Haar, C. L. Stern, T. J. Marks, Organometallics 1996, 15,
1765 1784; c) K. C. Hultzsch, T. P. Spaniol, J. Okuda, Organometal-
lics 1997, 16, 4845 4856; d) J. C. Yoder, M. W. Day, J. E. Bercaw,
Organometallics 1998, 17, 4946 4958; e) J. Eppinger, Ph.D. thesis,
Technische Universit‰t M¸nchen (Germany), 1999.
[25] See for example: a) P. B. Hitchcock, M. F. Lappert, R. G. Smith, Inorg.
Chim. Acta 1987, 139, 183 184; b) H. Schumann, J. Winterfeld, R. D.
Kohn, L. Esser, J. Sun, A. Dietrich, Chem. Ber. 1993, 126, 907 912;
d) G. B. Deacon, B. M. Gatehouse, Q. Shen, G. N. Ward, E. R. T.
Tiekink, Polyhedron 1993, 12, 1289 1294; e) R. J. Butcher, D. L.
Clark, S. K. Grumbine, R. L. Vincent-Hollis, B. L. Scott, J. G. Watkin,
Inorg. Chem. 1995, 34, 5468 5476; f) D. L. Clark, G. B. Deacon, T.
Feng, R. V. Hollis, B. L. Scott, B. W. Skelton, J. G. Watkin, A. H.
White, Chem. Commun. 1996, 1729 1730; g) D. L. Clark, R. V. Hollis,
B. L. Scott, J. G. Watkin, Inorg. Chem. 1996, 35, 667 674; h) W. J.
Evans, M. Ansari, J. W. Ziller, S. I. Khan, J. Organomet. Chem. 1998,
553, 141 148; i) H. C. Aspinall, J. F. Bickley, J. L. M. Dwyer, R. V.
Kelly, A. Steiner, Organometallics 2000, 19, 5416 5423; j) G. B.
Deacon, T. Feng, C. M. Forsyth, A. Gitlits, D. C. R. Hockless, Q. Shen,
B. W. Skelton, A. H. White, J. Chem. Soc. Dalton Trans. 2000, 961
966.
[9] C. J. Schaverien, N. Meijboom, A. G. Orpen, J. Chem. Soc. Chem.
Commun. 1992, 124 126.
[10] a) A. H. Hoveyda, R. R. Schrock, Chem. Eur. J. 2001, 7, 945 950;
b) J. B. Alexander, D. S. La, D. R. Cefalo, A. H. Hoveyda, R. R.
Schrock, J. Am. Chem. Soc. 1998, 120, 4041 4042; c) J. B. Alexander,
R. R. Schrock, W. M. Davis, K. C. Hultzsch, A. H. Hoveyda, J. H.
Houser, Organometallics 2000, 19, 3700 3715; d) S. S. Zhu, D. R.
Cefalo, D. S. La, J. Y. Jamieson, W. M. Davis, A. H. Hoveyda, R. R.
Schrock, J. Am. Chem. Soc. 1999, 121, 8251 8259; e) W. C. Tsang,
R. R. Schrock, A. H. Hoveyda, Organometallics 2001, 20, 5658 5669.
[11] H2(Biphen) is commercially available from Strem Chemicals, Inc. in
enantiopure form. Enantiopure binaphthol is available for a price of
ca. 800 E per kg from Reuter Chemische Apparatebau KG (RCA),
Freiburg, Germany.
[26] a) W. J. Evans, T. J. Boyle, J. W. Ziller, Organometallics 1993, 12,
3998 4009; b) R. Anwander, J. Eppinger, I. Nagl, W. Scherer, M.
Tafipolsky, P. Sirsch, Inorg. Chem. 2000, 39, 4713 4720; c) C. E.
Daitch, P. D. Hampton, E. N. Duesler, T. M. Alam, J. Am. Chem. Soc.
1996, 118, 7769 7773.
[27] K. C. Hultzsch, P. Voth, K. Beckerle, T. P. Spaniol, J. Okuda, Organo-
metallics 2000, 19, 228 243, and references therein.
À
[12] D. C. Bradley, J. S. Ghotra, F. A. Hart, J. Chem. Soc. Dalton Trans.
1973, 1021 1023.
[13] Additionally, all attempts to prepare biphenolate or binaphtholate
complexes of any of the ligands discussed here by salt metathesis have
failed so far.
[14] Ligands given without configuration are racemates.
[15] R. Anwander, O. Runte, J. Eppinger, G. Gerstberger, E. Herdtweck,
M. Spiegler, J. Chem. Soc. Dalton Trans. 1998, 847 858.
[16] Similar to observations made by Tilley on (S)-[{2,2'-bis(tert-butyl-
dimethylsilylamido)-6,6'-dimethylbiphenyl}YMe(thf)2], see: T. I.
Gountchev, T. D. Tilley, Organometallics 1999, 18, 5661 5667.
[17] R. D. Shannon, Acta Crystallogr. 1976, A32, 751 767.
[18] a) The identity of a homochiral dimeric lanthanum complex [La((R)-
biphen){CH(SiMe3)2}]2 has been proven by single-crystal X-ray
diffraction: D. V. Gribkov, F. Hampel, K. C. Hultzsch, unpublished
results; b) However, (R,S)-3a dissociates to 2a to a small extent
(10%) upon heating to 1008C.
[19] a) D. S. Lingenfelter, R. C. Helgeson, D. J. Cram, J. Org. Chem. 1981,
46, 393 406; b) P. Wipf, J.-K. Jung, J. Org. Chem. 2000, 65, 6319 6337.
[20] a) P. J. Cox, W. Wang, V. Snieckus, Tedrahedron Lett. 1992, 33, 2253
2256; b) K. Maruoka, N. Murase, H. Yamamoto, J. Org. Chem. 1993,
58, 2938 2939; c) K. Ishihara, H. Yamamoto, J. Am. Chem. Soc. 1994,
116, 1561 1562; d) W.-S. Huang, Q.-S. Hu, L. Pu, J. Org. Chem. 1998,
[28] a) [La{N(SiMe3)2}3(OPPh3)]: La N 2.38(2) 2.41(2) ä and [La{N-
À
(SiMe3)2}2(OPPh3)]2(m-O2): La N 2.37(2), 2.49(2) ä, see: D. C. Brad-
ley, J. S. Ghotra, F. A. Hart, M. B. Hursthouse, P. R. Raithby, J. Chem.
Soc. Dalton Trans. 1977, 1166 1172; b) [Cp*2La(NHMe)(H2NMe)]:
À
La N 2.31(2) ä, see: ref. [5a]; c) [Li(DME)3][(MeCp)La(NPh2)3]:
À
La N 2.443(7) 2.469(8) ä, see: J. Guan, S. Jin, Y. Lin, Q. Shen,
Organometallics 1992, 11, 2483 2487; d) [La{N(SiMe3)2}2(PPh2)-
À
(OPPh3)2]2: La N 2.40(1) ä, see: H. C. Aspinall, S. R. Moore,
A. K. Smith, J. Chem. Soc. Dalton Trans. 1992, 153 156; e) [La-
À
(NiPr2)2{m-P(C6H4-2-OMe)2}Li(thf)]: La N 2.30(1) ä, see: H. C.
Aspinall, S. R. Moore, A. K. Smith, J. Chem. Soc. Dalton Trans.
À
1993, 993 996; f) [La{N(SiHMe2)2}3(thf)2] (1b): La N 2.395(5)
2.416(5) ä, see ref. [15]; g) [{PhNC(C6H4-4-Me)N(CH2CH2-2-
À
C5H4N)}2La{N(SiHMe2)2}]: La N 2.453(4) ä, see: K. Kincaid, C. P.
Gerlach, J. R. Hagadorn, G. D. Whitener, A. Shafir, J. Arnold,
Organometallics 1999, 18, 5360 5366; h) [{Me2Si(C5Me4)2}La{N-
À
(SiHMe2)2}]: La N 2.449(3) ä, see: J. Eppinger, M. Spiegler, W.
Hieringer, W. A. Herrmann, R. Anwander, J. Am. Chem. Soc. 2000,
À
122, 3080 3096; i) [La{N(SiMe3)2}2(m-I)(thf)]2: La N 2.331(8),
2.352(9) ä, see: J. Collin, N. Giuseppone, N. Jaber, A. Domingos,
L. Maria, I. Santos, J. Organomet. Chem. 2001, 628, 271 274;
À
j) [{(Me3Si)2N}C(NC6H11)2La{N(SiMe3)2}]: La N(SiMe3)2 2.377(3),
2.382(3) ä, see: G. R. Giesbrecht, G. D. Whitener, J. Arnold, J. Chem.
Chem. Eur. J. 2003, 9, 4796 4810
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