False minima in X-ray structure solutions associated with a 'partial polar ambiguity': Single crystal X-ray and neuron diffraction studies on the eight-coordinate tungsten hydride complexes, W(PMe3)4H2X2 (X = F, Cl, Br, I) and W(PMe3)4H2F(FHF)

Journal of the American Chemical Society

Volumn 120, Issue 18, 1998, Pages 4372-4387

  Murphy, Vincent J ^a   Rabinovich, Daniel ^a   Hascall, Tony ^a   Klooster, Wim T ^b   Koetzle, Thomas F ^b   Parkin, Gerard ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

^b BROOKHAVEN NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX; TUNGSTEN DERIVATIVE;

ARTICLE; COMPLEX FORMATION; CONFORMATION; NEUTRON RADIATION; X RAY CRYSTALLOGRAPHY; X RAY DIFFRACTION;

EID: 0032513728     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja974086g     Document Type: Article

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30. g (a) Kanellakopulos, B.; Nuber, B.; Raptis, K.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1989, 28, 1055. (b) Burrell, A. K.; Cotton, F. A.; Daniels, L. M.; Petricek, V. Inorg. Chem. 1995, 34, 4253-4255. (c) Balch, A. L.; Olmstead, M. M.; Safari, N. Inorg. Chem. 1993, 32, 291-296. (d) Wood, F. E.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 1983, 105, 6332-6334. (e) Marsh, R. E.; Olmstead, M. M.; Schaefer, W. P.; Schomaker, V. Inorg. Chem. 1993, 32, 4658-4659. (f) Irving, A.; Irving, H. M. N. H. J. Crystallogr. Spectrosc. Res. 1988,18, 439-446. (g) Kapon, M.; Herbstein, F. H. Acta Crystallogr. 1995, B51, 108-113.
31. g (a) Kanellakopulos, B.; Nuber, B.; Raptis, K.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1989, 28, 1055. (b) Burrell, A. K.; Cotton, F. A.; Daniels, L. M.; Petricek, V. Inorg. Chem. 1995, 34, 4253-4255. (c) Balch, A. L.; Olmstead, M. M.; Safari, N. Inorg. Chem. 1993, 32, 291-296. (d) Wood, F. E.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 1983, 105, 6332-6334. (e) Marsh, R. E.; Olmstead, M. M.; Schaefer, W. P.; Schomaker, V. Inorg. Chem. 1993, 32, 4658-4659. (f) Irving, A.; Irving, H. M. N. H. J. Crystallogr. Spectrosc. Res. 1988,18, 439-446. (g) Kapon, M.; Herbstein, F. H. Acta Crystallogr. 1995, B51, 108-113.
32. g (a) Kanellakopulos, B.; Nuber, B.; Raptis, K.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1989, 28, 1055. (b) Burrell, A. K.; Cotton, F. A.; Daniels, L. M.; Petricek, V. Inorg. Chem. 1995, 34, 4253-4255. (c) Balch, A. L.; Olmstead, M. M.; Safari, N. Inorg. Chem. 1993, 32, 291-296. (d) Wood, F. E.; Olmstead, M. M.; Balch, A. L. J. Am. Chem. Soc. 1983, 105, 6332-6334. (e) Marsh, R. E.; Olmstead, M. M.; Schaefer, W. P.; Schomaker, V. Inorg. Chem. 1993, 32, 4658-4659. (f) Irving, A.; Irving, H. M. N. H. J. Crystallogr. Spectrosc. Res. 1988,18, 439-446. (g) Kapon, M.; Herbstein, F. H. Acta Crystallogr. 1995, B51, 108-113.
33. The phrase "false minimum" is used in this paper to refer specifically to a refinement which yields the incorrect location of correctly assigned atoms in the correct space group. Thus, refinements which involve, for example, incorrect atom assignments or incorrect space groups are not false minima of the type discussed in this paper.
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41. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
42. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
43. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
44. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
45. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
46. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
47. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
48. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
49. 2 and related studies, see: (a) Abu-Hasanayn, F.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 1993, 115, 8019-8023. (b) Abu-Hasanayn, F.; Goldman, A. S.; Krogh-Jespersen, K. Inorg. Chem. 1994, 22, 5122-5130. (c) Wang, K.; Rosini, G. P.; Nolan, S. P.; Goldman, A. S. J. Am. Chem. Soc. 1995, 117, 5082-5088. (d) Musaev, D. G.; Morokuma, K. J. Organomet. Chem. 1995, 504, 93-105. (e) Bakhmutov, V. I.; Bertrán, J.; Esteruelas, M. A.; Lledós, A.; Maseras, F.; Modrego, J.; Oro, L. A.; Sola, E. Chem. Eur. J. 1996, 2, 815-825. (f) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214. (g) Gusev, D. G.; Bakhmutov, V. I.; Grushin, V. V.; Vol'pin, M. E. Inorg. Chim. Acta 1990, 177, 115-120. (h) Hostetler, M. J.; Bergman, R. G. J. Am. Chem. Soc. 1992, 114, 7629-7636. (i) Lee, D. W.; Jensen, C. M. Inorg. Chim. Acta 1997, 259, 359-362. (j) Bender, B. R.; Kubas, G. J.; Jones, L. H.; Swanson, B. I.; Eckert, J.; Capps, K. B.; Hoff, C. D. J. Am. Chem. Soc. 1997, 119, 9179-9190.
50. (a) Green, M. L. H.; Parkin, G.; Chen, M.; Prout, K. J. Chem. Soc., Chem. Commun. 1984, 1400-1402.
51. (b) Green, M. L. H.; Parkin, G.; Chen, M.; Prout, K. J. Chem. Soc., Dalton Trans. 1986, 2227-2236.
52. Sharp, P. R.; Frank, K. G. Inorg. Chem. 1985, 24, 1808-1813.
53. 2 was first described in the Ph.D. Thesis of P. R. Sharp, Massachusetts Institute of Technology, 1980. We thank Professor R. R. Schrock for bringing this information to our attention.
54. 2. See: (a) Luetkens, M. L., Jr.; Huffman, J. C; Sattelberger, A. P. J. Am. Chem. Soc. 1983, 105, 4474-4475. (b) Luetkens, M. L., Jr.; Elcesser, W. L.; Huffman, J. C.; Sattelberger, A. P. Inorg. Chem. 1984, 23, 1718-1726.
55. 2. See: (a) Luetkens, M. L., Jr.; Huffman, J. C; Sattelberger, A. P. J. Am. Chem. Soc. 1983, 105, 4474-4475. (b) Luetkens, M. L., Jr.; Elcesser, W. L.; Huffman, J. C.; Sattelberger, A. P. Inorg. Chem. 1984, 23, 1718-1726.
56. b (a) Rothfuss, H.; Huffman, J. C.; Caulton, K. G. Inorg. Chem. 1994, 33, 2946-2953. (b) Crevier, T. J.; Mayer, J. M. J. Am. Chem. Soc. 1997, 119, 8485-8491.
57. b (a) Rothfuss, H.; Huffman, J. C.; Caulton, K. G. Inorg. Chem. 1994, 33, 2946-2953. (b) Crevier, T. J.; Mayer, J. M. J. Am. Chem. Soc. 1997, 119, 8485-8491.
58. Chiu, K. W.; Lyons, D.; Wilkinson, G.; Thornton-Pett, M.; Hursthouse, M. B. Polyhedron 1983, 2, 803-810.
59. 2 with alcohols, see ref 17b.
60. 2Ph. See: Fakley, M. E.; Richards, R. L. Transition Met. Chem. 1982, 7, 1-2.
61. 2)H with HX. See: Karsch, H. H. Chem. Ber. 1977, 110, 2222-2235.
62. 2; LiI, however, can achieve this transformation. See: Rothfuss, H.; Gusev, D. G.; Caulton, K. G. Inorg. Chem. 1995, 34, 2894-2901.
63. 2 with either LiF or AgF were unsuccessful.
64. 3].
65. For reviews on eight-coordination, see for example: (a) Lippard, S. J. Prog, Inorg. Chem. 1967, 8, 109-193. (b) Drew, M. G. B. Coord. Chem. Rev. 1977, 24, 179-275. (c) Burdett, J. K.; Hoffmann, R.; Fay, R. C. Inorg. Chem. 1978, 17, 2553-2568. (d) Keppert, D. L. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: New York, 1987; Vol. 1, Chapter 2, pp 31-107.
66. For reviews on eight-coordination, see for example: (a) Lippard, S. J. Prog, Inorg. Chem. 1967, 8, 109-193. (b) Drew, M. G. B. Coord. Chem. Rev. 1977, 24, 179-275. (c) Burdett, J. K.; Hoffmann, R.; Fay, R. C. Inorg. Chem. 1978, 17, 2553-2568. (d) Keppert, D. L. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: New York, 1987; Vol. 1, Chapter 2, pp 31-107.
67. For reviews on eight-coordination, see for example: (a) Lippard, S. J. Prog, Inorg. Chem. 1967, 8, 109-193. (b) Drew, M. G. B. Coord. Chem. Rev. 1977, 24, 179-275. (c) Burdett, J. K.; Hoffmann, R.; Fay, R. C. Inorg. Chem. 1978, 17, 2553-2568. (d) Keppert, D. L. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: New York, 1987; Vol. 1, Chapter 2, pp 31-107.
68. For reviews on eight-coordination, see for example: (a) Lippard, S. J. Prog, Inorg. Chem. 1967, 8, 109-193. (b) Drew, M. G. B. Coord. Chem. Rev. 1977, 24, 179-275. (c) Burdett, J. K.; Hoffmann, R.; Fay, R. C. Inorg. Chem. 1978, 17, 2553-2568. (d) Keppert, D. L. In Comprehensive Coordination Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press: New York, 1987; Vol. 1, Chapter 2, pp 31-107.
69. Lenenko, V. S.; Yanovskii, A. I.; Struchkov, Yu. T.; Shur, V. B.; Vol'pin, M. E. Sov. J. Coord. Chem. 1986, 12, 367-373.
70. Dadkhah, H.; Kashef, N.; Richards, R. L.; Hughes, D. L.; Pombeiro, A. J. L. J. Organomet. Chem. 1983, 255, C1-C4.
71. 2 was originally described (ref 16) in space group Cc, but it was later refined in the centrosymmetric space group C2/c. See: Marsh, R. E.; Slagle, K. M. Inorg. Chem. 1985, 24, 2114-2115.
72. 2MM′XX′ spin system. See ref 17a.
73. (a) Meakin, P.; Guggenberger, L. J.; Peet, W. G.; Muetteries, E. L.; Jesson, J. P. J. Am. Chem. Soc. 1973, 95, 1467-1474.
74. (b) Chiu, K. W.; Jones, R. A.; Wilkinson, G.; Galas, A. M. R.; Hursthouse, M. B.; Abdul-Malik, K. M. J. Chem. Soc., Dalton Trans. 1981, 1204-1211.
75. For other accounts of fluxionality in eight-coordinate complexes, see ref 25b and: Muetterties, E. L. Acc. Chem. Res. 1970, 3, 266-273.
76. CSD Version 5.13: 3D Search and Research Using the Cambridge Structural Database, Allen, F. H.; Kennard, O. In Chem. Design Automation News 1993, 8(1), 1, 31-37.
77. c (a) Morino, Y.; Uehara, H. J. Chem. Phys. 1966, 45, 4543-4550. (b) Clearfield, A.; Warner, D. K.; Saldarriaga-Molina, C. H.; Ropal, R.; Bernal, I. Can. J. Chem. 1975, 53, 1622-1629. (c) Huffman, J. C.; Moloy, K. G.; Marsella, J. A.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 3009-3014.
78. c (a) Morino, Y.; Uehara, H. J. Chem. Phys. 1966, 45, 4543-4550. (b) Clearfield, A.; Warner, D. K.; Saldarriaga-Molina, C. H.; Ropal, R.; Bernal, I. Can. J. Chem. 1975, 53, 1622-1629. (c) Huffman, J. C.; Moloy, K. G.; Marsella, J. A.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 3009-3014.
79. c (a) Morino, Y.; Uehara, H. J. Chem. Phys. 1966, 45, 4543-4550. (b) Clearfield, A.; Warner, D. K.; Saldarriaga-Molina, C. H.; Ropal, R.; Bernal, I. Can. J. Chem. 1975, 53, 1622-1629. (c) Huffman, J. C.; Moloy, K. G.; Marsella, J. A.; Caulton, K. G. J. Am. Chem. Soc. 1980, 102, 3009-3014.
80. It is worth noting that the value to be adopted for the covalent radius of fluorine has been a subject of much debate, due to the fact that all bonds to fluorine have considerable ionic character. See: Robinson, E. A.; Johnson, S. A.; Tang, T.-H.; Gillespie, R. J. Inorg. Chem. 1997, 36, 3022-3030.
81. 2 [2.496 Å].
82. 2 (X = F, Cl, Br, I) suggests that the formal charges on the tungsten centers do not vary significantly. See: Haaland, A. Angew. Chem., Int. Ed. Engl. 1989, 25, 992-1007.
83. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
84. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
85. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
86. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
87. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
88. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
89. g (a) Dean, J. A. Lange's Handbook of Chemistry, 13th ed.; New York, 1985; pp 3-126. (b) Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford. (c) Moeller, T. Inorganic Chemistry: An Advanced Textbook; Wiley: New York; p 135. (d) Batsanov, S. S. Russ. Chem. Bull. 1995, 44, 2245-2251. (e) Moeller, T. Inorganic Chemistry: A Modern Introduction; Wiley: New York; p 71. (f) Cambridge Structural Database System: Getting Started; 1994; Appendix E. (g) Porterfield, W. W. Inorganic Chemistry: A Unified Approach. 2nd ed.; Academic Press: New York; Table 4.4.
90. c,d (a) Schomaker, V.; Stevenson, D. P. J. Am. Chem. Soc. 1941, 63, 37-40. (b) Pauling L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, 1960. (c) Wells, A. F. J. Chem. Soc. 1949, 55-67. (d) Wells, A. F. Structural Inorganic Chemistry, 5th ed.; Oxford University Press: London, 1984; pp 287-291.
91. c,d (a) Schomaker, V.; Stevenson, D. P. J. Am. Chem. Soc. 1941, 63, 37-40. (b) Pauling L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, 1960. (c) Wells, A. F. J. Chem. Soc. 1949, 55-67. (d) Wells, A. F. Structural Inorganic Chemistry, 5th ed.; Oxford University Press: London, 1984; pp 287-291.
92. c,d (a) Schomaker, V.; Stevenson, D. P. J. Am. Chem. Soc. 1941, 63, 37-40. (b) Pauling L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, 1960. (c) Wells, A. F. J. Chem. Soc. 1949, 55-67. (d) Wells, A. F. Structural Inorganic Chemistry, 5th ed.; Oxford University Press: London, 1984; pp 287-291.
93. c,d (a) Schomaker, V.; Stevenson, D. P. J. Am. Chem. Soc. 1941, 63, 37-40. (b) Pauling L. The Nature of The Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, 1960. (c) Wells, A. F. J. Chem. Soc. 1949, 55-67. (d) Wells, A. F. Structural Inorganic Chemistry, 5th ed.; Oxford University Press: London, 1984; pp 287-291.
94. It should be noted that Bau has also reported a value of 1.743(6) Å for the average terminal W-H bond length. See: Bau, R.; Drabnis, M. H. Inorg. Chim. Acta 1997, 259, 27-50.
95. Caulton, K. G. New J. Chem. 1994, 18, 25-41.
96. It is also possible that steric interactions within the eight-coordinate complexes may result in longer bond lengths.
97. The single bond metallic radii described by Pauling refer to "single covalent bonds for which the bond orbitals have the same hybrid character as in the metals themselves". See ref 38b, p 256.
98. Murphy, V. J.; Rabinovich, D.; Parkin, G. J. Am. Chem. Soc. 1995, 117, 9762-9763.
99. Minqin, C.; Prout, K. J. Struct. Chem. 1986, 5, 23-27.
100. Curtin, D. Y.; Paul, I. C. Chem. Rev. 1981, 81, 525-541.
101. 1 (No. 36) is nonenantiomorphous (it contains both mirror and glide planes).
102. a (a) Zalkin, A.; Hopkins, T. E.; Templeton, D. H. Inorg. Chem. 1966, 5, 1767-1770. (b) Ueki, T.; Zalkin, A.; Templeton, D. H. Acta Crystallogr. 1966, 20, 836-841. (c) Templeton, L. K.; Templeton, D. H.; Zalkin, A.; Ruben, H. W. Acta Crystallogr. 1982, B38, 2155-2159.
103. a (a) Zalkin, A.; Hopkins, T. E.; Templeton, D. H. Inorg. Chem. 1966, 5, 1767-1770. (b) Ueki, T.; Zalkin, A.; Templeton, D. H. Acta Crystallogr. 1966, 20, 836-841. (c) Templeton, L. K.; Templeton, D. H.; Zalkin, A.; Ruben, H. W. Acta Crystallogr. 1982, B38, 2155-2159.
104. a (a) Zalkin, A.; Hopkins, T. E.; Templeton, D. H. Inorg. Chem. 1966, 5, 1767-1770. (b) Ueki, T.; Zalkin, A.; Templeton, D. H. Acta Crystallogr. 1966, 20, 836-841. (c) Templeton, L. K.; Templeton, D. H.; Zalkin, A.; Ruben, H. W. Acta Crystallogr. 1982, B38, 2155-2159.
105. For other discussions of the polar dispersion error, see: (a) Messmer, G. G.; Amma, E. L.; Ibers, J. A. Inorg. Chem. 1967, 6, 725-730. (b) Cotton, F. A.; Foxman, B. M, Inorg. Chem. 1968, 7, 1784-1792. (c) Anomalous Scattering; Ramaseshan, S., Abrahams, S. C., Eds.; International Union of Crystallography, Munksgaard International Publishers: Penhagen, 1975. (d) Cruickshank, D. W. J.; McDonald, W. S. Acta Crystallogr. 1967, 23, 9-11.
106. For other discussions of the polar dispersion error, see: (a) Messmer, G. G.; Amma, E. L.; Ibers, J. A. Inorg. Chem. 1967, 6, 725-730. (b) Cotton, F. A.; Foxman, B. M, Inorg. Chem. 1968, 7, 1784-1792. (c) Anomalous Scattering; Ramaseshan, S., Abrahams, S. C., Eds.; International Union of Crystallography, Munksgaard International Publishers: Penhagen, 1975. (d) Cruickshank, D. W. J.; McDonald, W. S. Acta Crystallogr. 1967, 23, 9-11.
107. For other discussions of the polar dispersion error, see: (a) Messmer, G. G.; Amma, E. L.; Ibers, J. A. Inorg. Chem. 1967, 6, 725-730. (b) Cotton, F. A.; Foxman, B. M, Inorg. Chem. 1968, 7, 1784-1792. (c) Anomalous Scattering;
108. For other discussions of the polar dispersion error, see: (a) Messmer, G. G.; Amma, E. L.; Ibers, J. A. Inorg. Chem. 1967, 6, 725-730. (b) Cotton, F. A.; Foxman, B. M, Inorg. Chem. 1968, 7, 1784-1792. (c) Anomalous Scattering; Ramaseshan, S., Abrahams, S. C., Eds.; International Union of Crystallography, Munksgaard International Publishers: Penhagen, 1975. (d) Cruickshank, D. W. J.; McDonald, W. S. Acta Crystallogr. 1967, 23, 9-11.
109. b-e The Flack x parameter has, however, been suggested to be the more reliable indicator of the correct absolute structure. Permissible values for x range from 0 for the correct absolute structure to 1 for the incorrect absolute structure; an intermediate value is indicative that the crystal is a racemic twin. (a) Rogers, D. Acta Crystallogr. 1981, A37, 734-741. (b) Flack, H. D. Acta Crystallogr. 1983, A39, 876-881. (c) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1987, A43, 75-78. (d) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1985, A41, 500-511. (e) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499-506.
110. b-e The Flack x parameter has, however, been suggested to be the more reliable indicator of the correct absolute structure. Permissible values for x range from 0 for the correct absolute structure to 1 for the incorrect absolute structure; an intermediate value is indicative that the crystal is a racemic twin. (a) Rogers, D. Acta Crystallogr. 1981, A37, 734-741. (b) Flack, H. D. Acta Crystallogr. 1983, A39, 876-881. (c) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1987, A43, 75-78. (d) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1985, A41, 500-511. (e) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499-506.
111. b-e The Flack x parameter has, however, been suggested to be the more reliable indicator of the correct absolute structure. Permissible values for x range from 0 for the correct absolute structure to 1 for the incorrect absolute structure; an intermediate value is indicative that the crystal is a racemic twin. (a) Rogers, D. Acta Crystallogr. 1981, A37, 734-741. (b) Flack, H. D. Acta Crystallogr. 1983, A39, 876-881. (c) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1987, A43, 75-78. (d) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1985, A41, 500-511. (e) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499-506.
112. b-e The Flack x parameter has, however, been suggested to be the more reliable indicator of the correct absolute structure. Permissible values for x range from 0 for the correct absolute structure to 1 for the incorrect absolute structure; an intermediate value is indicative that the crystal is a racemic twin. (a) Rogers, D. Acta Crystallogr. 1981, A37, 734-741. (b) Flack, H. D. Acta Crystallogr. 1983, A39, 876-881. (c) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1987, A43, 75-78. (d) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1985, A41, 500-511. (e) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499-506.
113. b-e The Flack x parameter has, however, been suggested to be the more reliable indicator of the correct absolute structure. Permissible values for x range from 0 for the correct absolute structure to 1 for the incorrect absolute structure; an intermediate value is indicative that the crystal is a racemic twin. (a) Rogers, D. Acta Crystallogr. 1981, A37, 734-741. (b) Flack, H. D. Acta Crystallogr. 1983, A39, 876-881. (c) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1987, A43, 75-78. (d) Bernardinelli, G.; Flack, H. D. Acta Crystallogr. 1985, A41, 500-511. (e) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499-506.
114. It should be noted that the relationship between the z coordinates of the true and false locations z(true) = -z(false) is only true because W is arbitrarily situated at z = 0. More generally, the relationship would be z(true) = z(W) - z(false), if W were not to be located at z = 0.
115. 3 ligands is crystallographically unique.
116. d (a) Arnold, J.; Tilley, T. D.; Rheingold, A. L.; Geib, S. J.; Arif, A. M. J. Am. Chem. Soc. 1989, 111, 149-164. (b) Rheingold, A. L. Acta Crystallogr. 1990, C46, 2374-2377. (c) Dias, H. V. R.; Huai, L.; Jin, W.; Bott, S. G. Inorg. Chem. 1995, 34, 1973-1974. (d) Kuchta, M. C.; Dias, H. V. R.; Bott, S. G.; Parkin, G. Inorg. Chem. 1996, 35, 943-948.
117. d (a) Arnold, J.; Tilley, T. D.; Rheingold, A. L.; Geib, S. J.; Arif, A. M. J. Am. Chem. Soc. 1989, 111, 149-164. (b) Rheingold, A. L. Acta Crystallogr. 1990, C46, 2374-2377. (c) Dias, H. V. R.; Huai, L.; Jin, W.; Bott, S. G. Inorg. Chem. 1995, 34, 1973-1974. (d) Kuchta, M. C.; Dias, H. V. R.; Bott, S. G.; Parkin, G. Inorg. Chem. 1996, 35, 943-948.
118. d (a) Arnold, J.; Tilley, T. D.; Rheingold, A. L.; Geib, S. J.; Arif, A. M. J. Am. Chem. Soc. 1989, 111, 149-164. (b) Rheingold, A. L. Acta Crystallogr. 1990, C46, 2374-2377. (c) Dias, H. V. R.; Huai, L.; Jin, W.; Bott, S. G. Inorg. Chem. 1995, 34, 1973-1974. (d) Kuchta, M. C.; Dias, H. V. R.; Bott, S. G.; Parkin, G. Inorg. Chem. 1996, 35, 943-948.
119. d (a) Arnold, J.; Tilley, T. D.; Rheingold, A. L.; Geib, S. J.; Arif, A. M. J. Am. Chem. Soc. 1989, 111, 149-164. (b) Rheingold, A. L. Acta Crystallogr. 1990, C46, 2374-2377. (c) Dias, H. V. R.; Huai, L.; Jin, W.; Bott, S. G. Inorg. Chem. 1995, 34, 1973-1974. (d) Kuchta, M. C.; Dias, H. V. R.; Bott, S. G.; Parkin, G. Inorg. Chem. 1996, 35, 943-948.
120. Such a phenomenon is related to the concept of homometric structures, i.e., different structures with the same Patterson Map. See: Patterson and Pattersons; Glusker J. P., Patterson, B. K., Rossi, M., Eds.; Oxford University Press: New York, 1987.
121. Spek, A. L. Acta Crystallogr. 1990, A46, C34.
122. For a review covering quantitative aspects of the interpretation of anisotropic displacement parameters, see: Dunitz, J. D.; Maverick, E. F.; Trueblood, K. N. Angew. Chem., Int. Ed. Engl. 1988, 27, 880-895.
123. 3 are the three main axes components of the thermal ellipsoid.
124. 1 for C(31), C(32), and C(33) are 5.95, 20.84, and 6.82, respectively. For comparison, the ratios for other carbon atoms are in the range 3.05 to 4.06.
125. 1 for P(1), P(2), and P(3) are 1.91, 1.48, and 2.17, respectively.
126. For example, Harlow's "ORTEP of the Year" award is an illustration of the fact that structures with unusual displacement parameters are frequently published. See ref 2f.
127. 2 is characterized by four intramolecular H⋯H contacts more than 0.25 Å less than the sum of the van der Waals radii (max = -1.28 Å) and two intermolecular H⋯H contacts more than 0.25 Å less than the sum of the van der Waals radii (max = -0.44 Å).
128. Hirshfeld, F. L. Acta Crystallogr. 1976, A32, 239-244.
129. For other articles concerned with similar tests, see: (a) Rosenfield, R. E.; Trueblood, K. N.; Dunitz, J. D. Acta Crystallogr. 1978, A34, 828-829. (b) Schomaker, V.; Trueblood, K. N. Acta Crystallogr. 1968, B24, 63-76.
130. For other articles concerned with similar tests, see: (a) Rosenfield, R. E.; Trueblood, K. N.; Dunitz, J. D. Acta Crystallogr. 1978, A34, 828-829. (b) Schomaker, V.; Trueblood, K. N. Acta Crystallogr. 1968, B24, 63-76.
131. Borman, S. Chem. Eng. News 1995, Oct 2, 27-29.
132. 1/n) is not polar.
133. For comparison, derived bond lengths for this refinement are as follows: W-P1 (2.458 Å), W-P2 (2.520 Å), W-P3 (2.480 Å), W-C11 (2.672 Å), W-C12 (2.591 Å), P1-C11 (1.786 Å), P1-C12 (1.768 Å), P2-C21 (1.637 Å), P2-C22 (1.893 Å), P3-C31 (1.779 Å), P3-C32 (1.788 Å), and P3-C33 (1.693 A̧).
134. For example, some of the isotropic thermal parameters refined to negative values and some were large.
135. 2F(FHF) for the purposes of our study.
136. 2F(FHF) will be reported together with details on the molybdenum system.
137. 1 for C(21), C(22), and C(32) are 5.80, 8.25, and 19.04, respectively. For comparison, the ratios for other carbon atoms are in the range 2.99 to 4.85.
138. 1 for C(21) and C(22) are 6.62 and 9.78, respectively.
139. 1 for P(1), P(2), and P(3) are 1.57, 1.68, and 1.56, respectively.
140. 2F(FHF) is characterized by three intramolecular H⋯H contacts more than 0.25 Å less than the sum of the van der Waals radii (max = -1.27 Å) and two intermolecular H⋯H contacts more than 0.25 Å less than the sum of the van der Waals radii (max = -0.28 Å).
141. 2F(FHF) is characterized by two intramolecular H⋯H contacts more than 0.25 Å less than the sum of the van der Waals radii (max = -0.33 Å).
142. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
143. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
144. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
145. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
146. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
147. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
148. For reviews on bifluoride salts, see: (a) Tuck, D. G. Progr. Inorg. Chem. 1968, 9, 161-194. (b) Emsley, J. Chem. Soc. Rev. 1980, 9, 91-124. (c) Hibbert, F.; Emsley, J. Adv. Phys. Org. Chem. 1990, 26, 255-379. (d) Hamilton, W. C.; Ibers, J. A. Hydrogen Bonding in Solids: Methods of Molecular Structure Determination; W. A. Benjamin, Inc.: New York, 1968. (e) Ault, B. S. Acc. Chem. Res. 1982, 15, 103-109. (f) Landrum, G. A.; Goldberg, N.; Hoffmann, R. J. Chem. Soc., Dalton Trans. 1997, 3605-3613. (h) Jeffrey, G. A. An Introduction to Hydrogen Bonding, Oxford University Press: New York, 1997.
149. Murphy, V. J.; Hascall, T.; Chen, J. Y.; Parkin, G. J. Am. Chem. Soc. 1996, 118, 7428-7429.
150. (a) Whittlesey, M. K.; Perutz, R. N.; Greener, B.; Moore, M. H. J. Chem. Soc., Chem. Commun. 1997, 187-188.
151. (b) Whittlesey, M. K.; Perutz, R. N.; Moore, M. H. J. Chem. Soc., Chem. Commun. 1996, 787-788.
152. (c) Whittlesey, M. K.; Perutz, R. N. Abstracts of 6th International Conference on the Chemistry of the Platinum Group Metals, York, UK, July 21-26, 1996; poster 80.
153. 2, has also been structurally characterized. See: Roesky, H. W.; Sotoodeh, M.; Xu, Y. M.; Schrumpf, F.; Noltemeyer, M. Z. Anorg. Allg. Chem. 1990, 580, 131-138.
154. b (a) Hintermann, S.; Pregosin, P. S.; Rüegger, H.; Clark, H. C. J. Organomet. Chem. 1992, 435, 225-234. (b) Coulson, D. R. J. Am. Chem. Soc. 1976, 98, 3111-3119.
155. b (a) Hintermann, S.; Pregosin, P. S.; Rüegger, H.; Clark, H. C. J. Organomet. Chem. 1992, 435, 225-234. (b) Coulson, D. R. J. Am. Chem. Soc. 1976, 98, 3111-3119.
156. Bondi, A. J. Phys. Chem. 1964, 68, 441-451.
157. Strong hydrogen bonds are typically characterized by A⋯B separations that are ≥0.25 Å less than the sum of the van der Waals radii. See ref 74c.
158. For comparison, the H-F bond length in HF is 0.918 Å. See ref 38b, p 226.
159. Peterson, S. W.; Levy, H. A. J. Phys. Chem. 1952, 56, 704-707.
160. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
161. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
162. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
163. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
164. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
165. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
166. For other examples in which M-F bonds participate in hydrogenbonding interactions, see: (a) Richmond, T. G. Coord. Chem. Rev. 1990, 105, 221-250. (b) Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373-431. (c) Osterberg, C. E.; King, M. A.; Arif, A. M.; Richmond, T. G. Angew. Chem., Int. Ed. Engl. 1990, 29, 888-890. (d) Osterberg, C. E.; Arif, A. M.; Richmond, T. G. J. Am. Chem. Soc. 1988, 110, 6903-6904. (e) Patel, B. P.; Crabtree, R. H. J. Am. Chem. Soc. 1996, 118, 13105-13106. (f) Ault, B. S. Inorg. Chem. 1991, 30, 2483-2487. (g) Herzog, A.; Roesky, H. W.; Jäger, F.; Steiner, A. J. Chem. Soc., Chem. Commun. 1996, 29-30.
167. 2 exhibits enhanced nucleophilicity. See refs 22 and 40.
168. F-F coupling of 152 Hz. See ref 76a.
169. (a) McDonald, T. R. R. Acta Crystallogr. 1960, 13, 113-124.
170. (b) Frevel, L. K.; Rinn, H. W. Acta Crystallogr. 1962, 15, 286.
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175. -1).
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177. Kuchta, M. C.; Parkin, G. New J. Chem. In press.
178. b (a) Jones, P. G. Acta Crystallogr. 1984, A40, 660-662. (b) Jones, P. G. Acta Crystallogr. 1986, A42, 57.
179. b (a) Jones, P. G. Acta Crystallogr. 1984, A40, 660-662. (b) Jones, P. G. Acta Crystallogr. 1986, A42, 57.
180. For other comments on absolute structure, see: (a) Jones, P. G.; Meyer-Bäse, K. Acta Crystallogr. 1986, A43, 79-80. (b) Jones, P. G. Acta Crystallogr. 1984, A40, 663-668. (c) Jones, P. G. Acta Crystallogr. 1986, C42, 924-925. (d) Jones, P. G.; Schelbach, R.; Schwarzmann, E.; Thöne, C. Acta Crystallogr. 1988, C44, 1196-1198. (e) Rogers, D. Acta Crystallogr. 1979, B35, 2823-2825.
181. For other comments on absolute structure, see: (a) Jones, P. G.; Meyer-Bäse, K. Acta Crystallogr. 1986, A43, 79-80. (b) Jones, P. G. Acta Crystallogr. 1984, A40, 663-668. (c) Jones, P. G. Acta Crystallogr. 1986, C42, 924-925. (d) Jones, P. G.; Schelbach, R.; Schwarzmann, E.; Thöne, C. Acta Crystallogr. 1988, C44, 1196-1198. (e) Rogers, D. Acta Crystallogr. 1979, B35, 2823-2825.
182. For other comments on absolute structure, see: (a) Jones, P. G.; Meyer-Bäse, K. Acta Crystallogr. 1986, A43, 79-80. (b) Jones, P. G. Acta Crystallogr. 1984, A40, 663-668. (c) Jones, P. G. Acta Crystallogr. 1986, C42, 924-925. (d) Jones, P. G.; Schelbach, R.; Schwarzmann, E.; Thöne, C. Acta Crystallogr. 1988, C44, 1196-1198. (e) Rogers, D. Acta Crystallogr. 1979, B35, 2823-2825.
183. For other comments on absolute structure, see: (a) Jones, P. G.; Meyer-Bäse, K. Acta Crystallogr. 1986, A43, 79-80. (b) Jones, P. G. Acta Crystallogr. 1984, A40, 663-668. (c) Jones, P. G. Acta Crystallogr. 1986, C42, 924-925. (d) Jones, P. G.; Schelbach, R.; Schwarzmann, E.; Thöne, C. Acta Crystallogr. 1988, C44, 1196-1198. (e) Rogers, D. Acta Crystallogr. 1979, B35, 2823-2825.
184. For other comments on absolute structure, see: (a) Jones, P. G.; Meyer-Bäse, K. Acta Crystallogr. 1986, A43, 79-80. (b) Jones, P. G. Acta Crystallogr. 1984, A40, 663-668. (c) Jones, P. G. Acta Crystallogr. 1986, C42, 924-925. (d) Jones, P. G.; Schelbach, R.; Schwarzmann, E.; Thöne, C. Acta Crystallogr. 1988, C44, 1196-1198. (e) Rogers, D. Acta Crystallogr. 1979, B35, 2823-2825.
185. Cruickshank subsequently considered the effect further and derived an expression to indicate the magnitude of the error in atomic coordinates that could be expected upon neglect of Δf″ and emphasized that the problem is not confined to the presence of heavy elements. See ref 48d.
186. In addition to the polar dispersion error, Jones has noted that it is possible for the incorrect absolute configuration to give rise to "ghost peaks" in a difference map that may be subsequently refined well as an atom. Specifically, Jones described an example where it was possible to refine an additional oxygen atom (which was assumed to be water of crystallization) for the incorrect absolute structure. However, the U value for this oxygen atom became prohibitively high for the inverted structure, clearly indicating that its inclusion is erroneous. See ref 91d.
187. 2] system, see: (a) Cotton, F. A.; Kohli, M.; Luck, R. L.; Silverton, J. V. Inorg. Chem. 1993, 32, 1868-1870. (b) Limberg, C.; Büchner, M.; Heinze, K.; Walter, O. Inorg. Chem. 1997, 36, 872-879.
188. 2] system, see: (a) Cotton, F. A.; Kohli, M.; Luck, R. L.; Silverton, J. V. Inorg. Chem. 1993, 32, 1868-1870. (b) Limberg, C.; Büchner, M.; Heinze, K.; Walter, O. Inorg. Chem. 1997, 36, 872-879.
189. For examples of species that may be considered to be bond-stretch "isomers" if differences in counterion or solvent of crystallization are neglected, see: (a) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV J. Chem. Soc., Chem. Commun. 1997, 421-422. (b) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV; Murillo, C. A. J. Am. Chem. Soc. 1997, 119, 10377-10381. (c) Köhn, R. D.; Seifert, G.; Kociok-Köhn, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 2879-2881.
190. For examples of species that may be considered to be bond-stretch "isomers" if differences in counterion or solvent of crystallization are neglected, see: (a) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV J. Chem. Soc., Chem. Commun. 1997, 421-422. (b) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV; Murillo, C. A. J. Am. Chem. Soc. 1997, 119, 10377-10381. (c) Köhn, R. D.; Seifert, G.; Kociok-Köhn, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 2879-2881.
191. For examples of species that may be considered to be bond-stretch "isomers" if differences in counterion or solvent of crystallization are neglected, see: (a) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV J. Chem. Soc., Chem. Commun. 1997, 421-422. (b) Cotton, F. A.; Daniels, L. M.; Jordan, G. T., IV; Murillo, C. A. J. Am. Chem. Soc. 1997, 119, 10377-10381. (c) Köhn, R. D.; Seifert, G.; Kociok-Köhn, G. Angew. Chem., Int. Ed. Engl. 1996, 35, 2879-2881.
192. For an example of a report in which oxo-chloro disorder was described, but was not considered as a rationalization of bond-stretch isomerism, see: Lincoln, S.; Koch, S. A. Inorg. Chem. 1986, 25, 1594-1602.
193. c (a) Cotton, F. A.; Rice, G. W. Inorg. Chem. 1978, 17, 688-692. (b) Donohue, J.; Goodman, S. H. Acta Crystallogr. 1967, 22, 352-354. (c) Wheeler, K. A.; Foxman, B. M. Mol. Cryst. Liq. Cryst. 1992, 211, 347-360.
194. c (a) Cotton, F. A.; Rice, G. W. Inorg. Chem. 1978, 17, 688-692. (b) Donohue, J.; Goodman, S. H. Acta Crystallogr. 1967, 22, 352-354. (c) Wheeler, K. A.; Foxman, B. M. Mol. Cryst. Liq. Cryst. 1992, 211, 347-360.
195. c (a) Cotton, F. A.; Rice, G. W. Inorg. Chem. 1978, 17, 688-692. (b) Donohue, J.; Goodman, S. H. Acta Crystallogr. 1967, 22, 352-354. (c) Wheeler, K. A.; Foxman, B. M. Mol. Cryst. Liq. Cryst. 1992, 211, 347-360.
196. (a) McNally, J. P.; Leong, V. S.; Cooper, N. J. In Experimental Organometallic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; Chapter 2, pp 6-23.
197. (b) Burger, B. J.; Bercaw, J. E. In Experimental Organometallic Chemistry; Wayda, A. L., Darensbourg, M. Y., Eds.; American Chemical Society: Washington, DC, 1987; Chapter 4, pp 79-98.
198. (c) Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-Sensitive Compounds, 2nd ed.; Wiley-Interscience: New York, 1986.
199. F-H = 8].
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