Adventures with substances containing metals in negative oxidation states

Inorganic Chemistry

Volumn 45, Issue 8, 2006, Pages 3167-3186

  Ellis, John E ^a  

^a University of Minnesota   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33646457204     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic052110i     Document Type: Review

References (273)

1. Adventure: An exciting, risky, and/or dangerous endeavor but one that may have romantic qualities, especially when it yields surprising new results! A seminar of the same title was presented by this writer on Feb 23, 2000, as the annual "Faculty Lecture" to the Faculty of Natural Sciences, Mathematics and Physics at the University of Pisa, Pisa, Italy.
2. Oxidation states, oxidation numbers, and valencies of metals in compounds are considered to be synonymous in this paper, as they have been in the past in many textbooks. For example, see: (a) Latimer, W. M.; Hildebrand, J. H. Reference Book of Inorganic Chemistry; Macmillan: New York, 1940; p 467.
3. (b) Pauling, L. General Chemistry; W. H. Freeman: San Francisco, 1947; pp 172-174, 188, 189, 196, 197, etc. Also, see refs 56-58, regarding formal oxidation state assignments, vide infra.
4. Joannis, A. C. R. Hebd. Seances Acad. Sci. 1891, 113, 795;
5. Joannis, A. C. R. Hebd. Seances Acad. Sci. 1892, 114, 585;
6. J. Chem. Soc., Abstr. 1892, 62, 275, 773.
7. Kraus, C. A. J. Am. Chem. Soc. 1907, 29, 1557.
8. (a) Zintl, E.; Goubeau, J.; Dullenkopf, W. Z. Phys. Chem. 1931, 154A, 1.
9. (b) Zintl, E.; Harder, A. Z. Phys. Chem. 1931, 154A, 47;
10. Chem. Abstr. 1931, 25, 3260.
11. 3), which formally contain As(I-), Sb(III-), Se(II-), and Te(II-), respectively. Also zinc telluride, likely in impure form, containing Te(II-), was obtained and acidified by Sir Humphry Davy in 1810 to obtain hydrogen telluride. See: Partington, J. R. A Textbook of Inorganic Chemistry, 5th ed.; Macmillan: London, 1937; p 536.
12. Corbett, J. D. Chem. Rev. 1985, 85, 383. This outstanding review contains a detailed chronological survey of "polyatomic Zintl anions" and related species.
13. (a) Corbett, J. D. Angew. Chem., Int. Ed. 2000, 39, 670.
14. (b) Li, X.; Kuznetsov, A. E.; Zhang, H.-F.; Boldyrev, A. I.; Wang, L.-S. Science 2001, 291, 859.
15. (c) Goicoechea, J. M.; Sevov, S. J. Am. Chem. Soc. 2004, 126, 6860 and references cited therein.
16. The following sources provide detailed information on the early history of gas-phase studies of monatomic metal anions: (a) Massey, H. S. W. Negative Ions, 2nd ed.; Cambridge University Press: London, 1950.
17. (b) Pritchard, H. O. Chem. Rev. 1953, 52, 529.
18. Arnot, F. L.; Milligan, J. C. Proc. R. Soc. London, Ser. A 1936, 156, 538.
19. Zollweg, R. J. J. Chem. Phys. 1969, 50, 4251.
20. Sloane, R. H.; Press, R. Proc. R. Soc. London, Ser. A 1938, 168, 284.
21. Sloane, R. H.; Love, H. M. Nature 1947, 159, 302.
22. You-Wu, T. Philos. Mag. 1936, 22, 837. This computed electron affinity for atomic Li, 0.54 eV, is not far from the currently accepted value, 0.62 eV; see ref 26a.
23. Peer, W. J.; Lagowski, J. J. J. Am. Chem. Soc. 1978, 100, 6260.
24. - in condensed phases.
25. - but is electronically quite different.
26. -". See: Reference 2a, pp 374 and 375.
27. Emsley, J. The Elements, 3rd ed.; Clarendon Press: Oxford, U.K., 1998; p 270.
28. (a) Rulfs, C. L.; Elving, P. J. J. Am. Chem. Soc. 1951, 73, 3287.
29. - underwent an apparent 8-electron reduction in aqueous perchloric or sulfuric acid.
30. 19b
31. (b) Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry, 2nd ed.; Interscience: New York, 1966; pp 978 and 979.
32. (a) Jolly, W. L. Modern Inorganic Chemistry, 2nd ed.; McGraw-Hill: New York, 1991; p 159.
33. (b) See: Reference 18, p 172.
34. Scheer, M. D.; Fine, J. J. Chem. Phys. 1967, 46, 3998.
35. Sommer, A. Nature 1943, 152, 215.
36. Spicer, W. E.; Sommer, A. H.; White, J. Phys. Rev. 1959, 115, 57.
37. Goodman, C. H. L. J. Phys. Chem. Solids 1958, 6, 305.
38. (a) Hotop, H.; Lineberger, W. C. J. Phys. Chem. Ref. Data 1975, 4, 539.
39. (b) Chen, E. C. M.; Wentworth, W. E. J. Chem. Educ. 1975, 52, 486.
40. (a) Cafasso, F.; Sundheim, B. R. J. Chem. Phys. 1959, 31, 809.
41. (b) Down, J. L.; Lewis, J.; Moore, B.; Wilkinson, G. J. Chem. Soc. 1959, 3767.
42. (c) Dye, J. L.; Dewald, R. R. J. Phys. Chem. 1964, 68, 135.
43. -, i.e., electrons trapped within approximately spherical boxes and stabilized by H bonding to ammonia molecules. See: Edwards, P. P. Adv. Inorg. Chem. Radiochem. 1982, 25, 135.
44. Matalon, S.; Golden, S.; Ottolenghi, M. J. Phys. Chem. 1969, 73, 3098.
45. Ebinghaus, H. Z. Naturforsch. 1964, 19A, 727.
46. (a) Dye, J. L. J. Phys. Chem. 1984, 88, 3842.
47. (b) Dye, J. L. Chemtracts: Inorg. Chem. 1993, 5, 243.
48. (a) Tehan, F. J.; Barnett, B. L.; Dye, J. L. J. Am. Chem. Soc. 1974, 96, 7203.
49. (b) Dye, J. L. J. Chem. Educ. 1977, 54, 332.
50. (c) Cryptand 222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane.
51. Dye, J. L. Sci. Am. 1977, 257 (1), 92. This popular article entitled "Anions of the Alkali Metals" includes a colored photograph showing gorgeous crystals of [Na(cryptand 222)][Na].
52. Gowik, P. K.; Klapötke, T. M. J. Chem. Soc., Chem. Commun. 1990, 1433.
53. Dietrich, B.; Lehn, J. M.; Sauvage, J. P. Tetrahedron Lett. 1969, 34, 2885 and 2889.
54. Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 7017.
55. (a) Kim, J.; Ichimura, A. S.; Huang, R. H.; Redko, M.; Phillips, R. C.; Jackson, J. E.; Dye, J. L. J. Am. Chem. Soc. 1999, 121, 10666.
56. (b) Redko, M. Y.; Jackson, J. E.; Huang, R. H.; Dye, J. L. J. Am. Chem. Soc. 2005, 127, 12416.
57. Redko, M. Y.; Vlassa, M.; Jackson, J. E.; Misiolek, A. W.; Huang, R. H.; Dye, J. L. J. Am. Chem. Soc. 2002, 124, 5928. The adamanzane is related to hexamethylenetetramine, where all methylenes have been replaced by propylene groups. Because of the flexibility of the propylene units, all four equivalent N atoms can point inward to form an approximate tetrahedral cage about the effectively trapped proton.
58. 6 have electron affinities that are larger than those of neutral atoms. See Reference 21a, pp 577-579.
59. Knecht, J.; Fischer, R.; Overhof, H.; Hensel, F. J. Chem. Soc., Chem. Commun. 1978, 905.
60. Tehrani, T. H.; Peer, W. J.; Lagowski, J. J.; Bard, A. J. J. Am. Chem. Soc. 1978, 100, 7768.
61. Batchelor, R. J.; Birchall, T.; Burns, R. C. Inorg. Chem. 1986, 25, 2009.
62. Jagganthan, R.; Wallace, D. B.; Lagowski, J. J. Inorg. Chem. 1985, 24, 113.
63. Tran, N. E.; Lagowski, J. J. Inorg. Chem. 2001, 40, 1067.
64. 38
65. Burns, R. C.; Corbett, J. D. J. Am. Chem. Soc. 1981, 103, 2627.
66. Pyykkö, P. Angew. Chem., Int. Ed. 2002, 41, 3573.
67. Mudring, A.-V.; Jansen, M.; Daniels, J.; Krämer, S.; Mehring, M.; Prates Ramalho, J. P.; Romero, A. H.; Parrinello, M. Angew. Chem., Int. Ed. 2002, 41, 120.
68. Ellis, J. E. Organometallics 2003, 22, 3322.
69. Karbov, A.; Nuss, J.; Weding, U.; Jansen, M. Angew. Chem., Int. Ed. 2003, 42, 4818.
70. Alexandri, L. E.; Bogdanovic, B.; Dürr, C.; Hackett, S. C.; Jones, D. J.; Kolb, U.; Lagarden, M.; Roziere, J.; Wilczov, U. Chem. - Eur. J. 1997, 3, 1710.
71. Alexandri, L. E.; Bogdanovic, B. In Active Metals; Fürstner, A., Ed.; VCH Publishers: New York, 1996; pp 299-338.
72. Ho, J.; Ervin, K. M.; Lineberger, W. C. J. Chem. Phys. 1990, 93, 6987 and references cited therein.
73. Seo, D.-K.; Corbett, J. D. Science 2001, 291, 841 and references cited therein.
74. Kuznetsov, A. E.; Corbett, J. D.; Wang, L.-S.; Boldyrev, A. I. Angew. Chem., Int. Ed. 2001, 40, 3369.
75. 58 Other ambiquities can arise with formal oxidation-state assignments, especially when metal-metal bonds involving different metals or identical metals having much different ligand sets are present. Malcolm Green has considered these and other difficulties with oxidation-state assignments in "A New Approach to the Formal Classification of Covalent Compounds of the Elements". See: Green, M. L. H. J. Organomet. Chem. 1995, 500, 127.
76. For more examples, see: Elschenbroich, Ch.; Salzer, A. Organometallics, 2nd ed.; VCH Publishers: Weinheim, Germany, pp 206-241, 252-279, and 348-369.
77. Jorgensen, C. K. Oxidation Numbers and Oxidation States; Springer-Verlag: New York, 1969.
78. 77 which are only known in solution.
79. 2-, although its ionic nature was not established until 1957. See ref 49 for more details.
80. 8, but the ionic nature of these species was not established until many years later. See ref 49 for more details.
81. Behrens, H. Angew Chem. 1955, 67, 521.
82. Ercoli, R.; Calderazzo, F.; Alberola, A. J. Am. Chem. Soc. 1960, 82, 2966.
83. Kruck, T.; Lang, W.; Engelmann, A. Angew. Chem., Int. Ed. Engl. 1965, 4, 148.
84. Kruck, T.; Prasch, A. Z. Anorg. Allg. Chem. 1969, 371, 1.
85. Muetterties, E. L.; Hirsekorn, F. J. J. Chem. Soc., Chem. Commun. 1973, 683.
86. Elschenbroich, Ch.; Gerson, F. J. Am. Chem. Soc. 1975, 97, 3556.
87. Jonas, K. Angew. Chem., Int. Ed. Engl. 1975, 14, 752.
88. Ellis, J. E.; Faltynek, R. A. J. Chem. Soc., Chem. Commun. 1975, 966.
89. Jonas, K.; Mynott, R.; Krüger, C.; Sekutowski, J. C.; Tsay, Y.-H. Angew. Chem., Int. Ed. Engl. 1976, 15, 767.
90. Hammer, R.; Klein, H.-F. Z. Naturforsch. 1977, 32B, 138.
91. Ellis, J. E.; Parnell, C. P.; Hagen, G. P. J. Am. Chem. Soc. 1978, 100, 3605.
92. Jonas, K.; Schieferstein, L.; Krüger, C.; Tsay, Y.-H. Angew. Chem., Int. Ed. Engl. 1979, 18, 550.
93. Bandy, J. A.; Berry, A.; Green, M. L. H.; Perutz, R. N.; Prout, K.; Verpeaux, J.-N. J. Chem. Soc., Chem. Commun. 1984, 729.
94. Bandy, J. A.; Prout, K.; Cloke, F. G. N.; de Lemos, H. C.; Wallis, J. M. J. Chem. Soc., Dalton Trans. 1988, 1475.
95. Warnock, G. F.; Cooper, N. J. Organometallics 1989, 8, 1826.
96. Corella, J. A., II; Thompson, R. L.; Cooper, N, J. Angew. Chem., Int. Ed. Engl. 1992, 31, 83.
97. Jonas, K.; Häselhoff, C.-C.; Goddard, R.; Krüger, C. Inorg. Chim. Acta 1992, 198-200, 533.
98. Cloke, F. G. N.; Hitchcock, P. B.; McCamley, A. J. Chem. Soc., Chem. Commun. 1993, 248.
99. Jang, M.; Ellis, J. E. Angew. Chem., Int. Ed. Engl. 1994, 33, 1965.
100. (a) Boulmaaz, S.; Mlakar, M.; Loss, S.; Schönberg, H.; Deblon, S.; Wöhrle, M.; Nespar, R.; Grützmacher, H. Chem. Commun. 1998, 2623.
101. -, where dppf = 1,1′-bis(diphenylphosphano)-ferrocene, has been reported: Longato, R.; Riello, L.; Bandoli, G.; Pilloni, G. Inorg. Chem. 1999, 38, 2818.
102. Mezailles, N.; Rosa, P.; Ricard, L.; Mathey, F.; LeFloch, P. Organometallics 2000, 19, 2941.
103. Brennessel, W. W.; Young, V. G., Jr.; Ellis, J. E. Angew. Chem., Int. Ed. 2002, 41, 1211.
104. 2 complexes.
105. (a) Daff, B. J.; Etienne, M.; Donnadieu, B.; Knottenbelt, S. Z.; McGrady, J. E. J. Am. Chem. Soc. 2002, 124, 3818 and references cited therein.
106. (b) Cloke, F. G. N.; deLemos, H. C.; Sameh, A. A. J. Chem. Soc., Chem. Commun. 1986, 1344.
107. Maher, J. M.; Fox, J. R.; Foxman, B. M.; Cooper, N. J. J. Am. Chem. Soc. 1984, 106, 2347.
108. (a) Herzog, S.; Zühlke, H. Z. Chem. 1966, 6, 382.
109. (b) McWhinnie, W. R.; Miller, J. D. Adv. Inorg. Chem. Radiochem. 1969, 12, 135.
110. (a) Holleman, A. F.; Wiberg, E. Inorganic Chemistry, 34th ed.; Academic Press: San Diego, CA, 2001; p 1336 and 1355.
111. (b) See: Reference 18, p 216.
112. (c) Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd ed.; Butterworth-Heinemann: Oxford, U.K., 1997; p 960.
113. (d) Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; John Wiley: New York, 1999; p 715. However, also see p 351 concerning such anionic complexes.
114. (a) Jørgensen was one of the first to question the presence of "negative-valent or subvalent" transition metals in these anionic bipyridyl complexes. See: Reference 58, pp 163-165.
115. 2-. See: König, E.; Herzog, S. J. Inorg. Nucl. Chem. 1970, 32, 585, 601, and 613.
116. Rosa, P.; Mezailles, N.; Ricard, L.; Mathey, F.; LeFloch, P. Angew. Chem., Int. Ed. 2000, 39, 1823.
117. Guggenberger, L. J.; Schrock, R. R. J. Am. Chem. Soc. 1975, 97, 6693. All COT rings are nonplanar in this complex.
118. Rosa, P.; Mezailles, N.; Ricard, L.; Mathey, F.; LeFloch, P.; Jean, Y. Angew. Chem., Int. Ed. 2001, 40, 1251.
119. 10 Co(I-) species.
120. 2- as an alkali-metal cryptand salt would be of substantial interest to see whether the dianion's structure will be effectively independent of the cation.
121. For an outstanding review on tmbp and related ligands and their coordination chemistry, see: Mezailles, N.; Mathey, F.; LeFloch, P. Prog. Inorg. Chem. 2001, 49, 455.
122. It should be emphasized that norbornene is a strained alkene and is thereby expected to be a stronger acceptor and a "less-innocent" ligand than ethylene, 1,5-cyclooctadiene, or other similar unstrained alkenes or nonconjugated dienes.
123. Similar Li-C distances are observed in bona fide organolithium compounds. See: Setzer, W. N.; Schleyer, P. v. R. Adv. Organomet. Chem. 1985, 24, 353.
124. Hieber, W. Adv. Organomet. Chem. 1970, 8, 1.
125. (a) Hieber, W.; Leutert, F. Ber. Dtsch. Chem. Ges. 1931, 64, 2832.
126. (b) Hieber, W.; Leutert, F. Naturwissenschaften 1931, 19, 360.
127. Hieber, W. Z. Elektrochem. 1934, 40, 158;
128. 2
129. Blanchard, A. A. Chem. Rev. 1940, 26, 409.
130. Halpern, J. Adv. Chem. Ser. 1968, 70, 1.
131. Foust, A. S.; Foster, M. S.; Dahl, L. F. J. Am. Chem. Soc. 1969, 91, 5631.
132. Foust, A. S.; Dahl, L. F. J. Am. Chem. Soc. 1970, 92, 7337.
133. Pnicogen or pnictide is often used as the family name for the group 15 elements, N, P, As, Sb, and Bi.
134. See: Reference 58, pp 237 and 238.
135. Jørgensen, C. K. Modern Aspects of Ligand Field Theory; North-Holland: Amsterdam, The Netherlands, 1971; pp 437-439.
136. (a) Ellis, J. E. J. Organomet. Chem. 1975, 86, 1.
137. (b) Ellis, J. E. J. Chem. Educ. 1976, 53, 2.
138. Hoffmann, R. Angew. Chem., Int. Ed. 1982, 21, 711.
139. Barraclough, C. G.; Lewis, J. J. Chem. Soc. 1960, 4842.
140. + is intrinsically a strong oxidant, it is totally incompatible with strongly reduced metal centers. Considerations of this type led to the Enemark-Feltham notation for transition-metal nitrosyls, which ignores the issue of meaningless oxidation-state assignments for compounds of this class. See: Enemark, J. H.; Feltham, R. D. Coord. Chem. Rev. 1974, 23, 339.
141. Dewar, J.; Jones, H. O. Proc. R. Soc. London, Ser. A 1905, 76, 558.
142. Krumholz, P.; Stettinger, H. M. A. J. Am. Chem. Soc. 1949, 71, 3035.
143. King, R. B. Adv. Organomet. Chem. 1964, 2, 157. This review entitled "Alkali Metal Derivatives of Metal Carbonyls" is an outstanding account of early syntheses of metal carbonyl anions.
144. Behrens, H. Adv. Organomet. Chem. 1980, 18, 1.
145. Wender, I.; Sternberg, H. W.; Orchin, M. J. Am. Chem. Soc. 1952, 74, 1216. To the best of my knowledge, this paper is the first to report on the use of alkali-metal amalgams to prepare metal carbonyl anions.
146. (a) Dighe, S. V.; Orchin, M. Inorg. Chem. 1962, 1, 956.
147. (b) King, R. B. J. Inorg. Nucl. Chem. 1963, 22, 1296.
148. For example, see: Rosenfeld, D. C.; Wolczanski, P. T.; Barakat, K. A.; Buda, C.; Cundari, T. R. J. Am. Chem. Soc. 2005, 127, 8262 and references cited therein.
149. Weber, R.; Behrens, H. Z. Anorg. Allg. Chem. 1957, 291, 122.
150. (a) Podall, H. E.; Prestridge, H. M.; Shapiro, H. J. Am. Chem. Soc. 1961, 83, 2057.
151. (b) Amiet, R. G.; Reeves, R. G.; Pettit, R. Chem. Commun. 1967, 1208.
152. Ward, J. S.; Pettit, R. Chem. Commun. 1970, 1419.
153. Ellis, J. E.; Hentges, S. G.; Kalina, D. G.; Hagen, G. P. J. Organomet. Chem. 1975, 97, 79.
154. Kaska, W. C. J. Am. Chem. Soc. 1968, 90, 6340.
155. HMPA has been shown to be a potent carcinogen to laboratory rats and must be handled with extreme care. See: Zapp, J. A. Science 1976, 190, 422.
156. Darensbourg, M. Y. Prog. Inorg. Chem. 1984, 33, 221.
157. Normant, H. Angew. Chem., Int. Ed. Engl. 1967, 6, 1046.
158. -. See: Edwards, P. P.; Guy, S. E.; Holton, D. M.; McFarlane, W. J. Chem. Soc., Chem. Commun. 1981, 1185.
159. Ellis, J. E.; Hagen, G. P. J. Am. Chem. Soc. 1974, 96, 7825.
160. Piper, T. S.; Wilkinson, G. J. Inorg. Nucl. Chem. 1956, 3, 104.
161. (a) Fischer, E. O.; Vigoureux, S. Chem. Ber. 1958, 91, 2205.
162. (b) Fischer, E. O.; Schneider, R. J. J. Angew. Chem., Int. Ed. Engl. 1967, 6, 569.
163. (a) Ellis, J. E.; Flom, E. A. J. Organomet. Chem. 1975, 99, 263.
164. -.
165. 132
166. 131
167. (a) Mein, F.; Kleinert, P.; Jehn, W. Naturwissenschaften 1952, 44, 34.
168. (b) Gorsich, R. D. J. Am. Chem. Soc. 1962, 84, 2486. Hein was the pioneer in the synthesis of mixed main group-transition metal carbonyl compounds, the first being reported in 1941.
169. See: Hein, F.; Pobloth, H. Z. Anorg. Allg. Chem. 1941, 248, 84.
170. Ellis, J. E.; Faltynek, R. A.; Hentges, S. G. J. Organomet. Chem. 1976, 120, 389.
171. Podall, H. E.; Giraitis, A. P. J. Org. Chem. 1961, 26, 2587.
172. Trifan, D. S.; Nicholas, L. J. Am. Chem. Soc. 1957, 79, 2746.
173. (a) Jonas, K. Angew. Chem., Int. Ed. Engl. 1985, 24, 295.
174. (b) Jonas, K. Pure Appl. Chem. 1990, 62, 1169.
175. (c) Jonas, K.; Häselhoff, C.-C.; Goddard, R.; Krüger, C. Inorg. Chim. Acta 1992, 198-200, 533 and references cited therein.
176. Ellis, J. E.; Faltynek, R. A. J. Chem. Soc., Chem. Commun. 1975, 966.
177. Ellis, J. E.; Faltynek, R. A. J. Am. Chem. Soc. 1977, 99, 1801.
178. Warnock, G. W.; Moodie, L. C.; Ellis, J. E. J. Am. Chem. Soc. 1989, 111, 2131.
179. Ellis, J. E. Adv. Organomet. Chem. 1990, 31, 1.
180. Ellis, J. E.; Palazzotto, M. C. J. Am. Chem. Soc. 1976, 98, 8264.
181. Ellis, J. E.; Hayes, T. E.; Stevens, R. E. J. Organomet. Chem. 1981, 216, 191.
182. Ellis, J. E. J. Am. Chem. Soc. 1981, 103, 6106.
183. Ellis, J. E.; Fjare, K. L.; Hayes, T. G. J. Am. Chem. Soc. 1981, 103, 6100.
184. Warnock, G. F.; Philson, S. B.; Ellis, J. E. J. Chem. Soc., Chem. Commun. 1984, 893.
185. See ref 141, Figure 9.
186. Warnock, G. F.; Ellis, J. E. J. Am. Chem. Soc. 1984, 106, 5016.
187. Rehder, D. J. Organomet. Chem. 1972, 37, 303.
188. Ellis, J. E.; Barger, P. T.; Winzenburg, M. L. J. Chem. Soc., Chem. Commun. 1977, 686.
189. Allen, J. M.; Brennessel, W. W.; Buss, C. E.; Ellis, J. E.; Minyaev, M. E.; Pink, M.; Warnock, G. F.; Winzenburg, M. L.; Young, V. G., Jr. Inorg. Chem. 2001, 40, 5279.
190. Ellis, J. E.; Barger, P. T.; Winzenburg, M. L.; Warnock, G. F. J. Organomet. Chem. 1990, 383, 521.
191. Jiang, L.; Xu, Q. J. Am. Chem. Soc. 2005, 127, 8906.
192. Herberhold, M.; Razavi, A. Angew. Chem., Int. Ed. Engl. 1972, 11, 1092.
193. -; effectively, the latter is a better leaving group than CO in this process. This simple concept should also work to good advantage in predicting the outcomes of reductive cleavage reactions of other classes of low-valent transition-metal complexes, provided the ligands do not undergo facile reduction. For example, most neutral or anionic metal carbonyl nitrosyls are not smoothly reduced perhaps because the coordinated nitrosyl groups are first changed to coordinated hyponitrites, which then suffer facile decomposition. See: Ellis, J. E.; Chen, Y.-S. Inorg. Chim. Acta 2000, 300-302, 675.
194. Darensbourg, M. Y. Prog. Inorg. Chem. 1984, 33, 221. This review has an outstanding account of the influence of contact ion pairing on the IR spectra of metal carbonyl anions.
195. Ellis, J. E.; Parnell, C. P.; Hagen, C. P. J. Am. Chem. Soc. 1978, 100, 3605.
196. Lin, J.-T.; Hagen, G. P.; Ellis, J. E. J. Am. Chem. Soc. 1983, 105, 2296.
197. Churchill, M. R.; Chang, S. W. Y. Inorg. Chem. 1979, 25, 145.
198. Lin, J.-T.; Hagen, G. P.; Ellis, J. E. Organometallics 1983, 2, 1145.
199. Lin, J.-T.; Hagen, G. P.; Ellis, J. E. Organometallics 1984, 3, 1288.
200. Ellis, J. E.; Davison, A. Inorg. Synth. 1976, 16, 68 and references cited therein.
201. Kündig, E. P.; Timms, P. L. J. Chem. Soc., Chem. Commun. 1977, 912.
202. Elschenbroich, Ch.; Möckel, R. Angew. Chem., Int. Ed. Engl. 1977, 16, 870.
203. Fischer, E. O.; Öfele, K. Chem. Ber. 1957, 90, 2532.
204. Henrici-Olivé, G.; Olivé, S. J. Am. Chem. Soc. 1970, 92, 4831.
205. Datta, S.; Wreford, S. S. Inorg. Chem. 1977, 16, 1134.
206. Dewey, C. G.; Ellis, J. E.; Fjare, K. L.; Pfahl, K. M.; Warnock, G. F. Organometallics 1983, 2, 388.
207. Ellis, J. E.; Warnock, G. F.; Barybin, M. V.; Pomije, M. K. Chem. - Eur. J. 1995, 1, 521.
208. Barybin, M. V.; Ellis, J. E.; Pomije, M. K.; Tinkham, M. L.; Warnock, G. F. Inorg. Chem. 1998, 37, 6518.
209. Barybin, M. V.; Pomije, M. K.; Ellis, J. E. Inorg. Chim. Acta 1998, 269, 58.
210. Liu, X.; Ellis, J. E. Inorg. Synth. 2004, 34, 96.
211. Calderazzo, F.; Englert, U.; Pampaloni, G.; Pelizzi, G.; Zamboni, R. Inorg. Chem. 1983, 22, 1865.
212. Calderazzo, F.; Pampaloni, G. J. Organomet. Chem. 1983, 250, C33.
213. 176
214. Warnock, G. F.; Fjare, K. L.; Ellis, J. E. J. Am. Chem. Soc. 1983, 105, 672.
215. See: Sikora, D. J.; Macomber, D. W.; Rausch, M. D. Adv. Organomet. Chem. 1986, 25, 317.
216. Pomije, M. K.; Kurth, C. J.; Ellis, J. E.; Barybin, M. V. Organometallics 1997, 16, 3582.
217. Beatty, R. P.; Datta, S.; Wreford, S. S. Inorg. Chem. 1979, 18, 3139.
218. Wreford, S. S.; Fischer, M. B.; Lee, J.-S.; James, E. J.; Nyburg, S. C. J. Chem. Soc., Chem. Commun. 1981, 458.
219. Domaille, P. J.; Harlow, R. L.; Wreford, S. S. Organometallics 1982, 1, 935.
220. Busby, R.; Klotzbücher, W.; Ozin, G. A. Inorg. Chem. 1977, 16, 822.
221. Cotton, F. A.; Matonic, J. H.; Murillo, C. A.; Petrukhina, M. A. Inorg. Chim. Acta 1998, 267, 173.
222. Chi, K.-M.; Frerichs, S. R.; Stein, B. K.; Blackburn, D. W.; Ellis, J. E. J. Am. Chem. Soc. 1988, 110, 163.
223. Ellis, J. E. Polyhedron 1989, 8, 1611.
224. Fischer, E. O.; Hafner, W. Z. Naturforsch. 1954, 9B, 503.
225. Kelsey, B. A.; Ellis, J. E. J. Am. Chem. Soc. 1986, 108, 5016.
226. Kelsey, B. A.; Ellis, J. E. J. Chem. Soc., Chem. Commun. 1986, 331.
227. Kelsey, B. A.; Ellis, J. E. Abstracts of Papers; 190th National Meeting of the American Chemical Society, Chicago, IL, Sept 8-13, 1985; American Chemical Society: Washington, DC, 1985; INOR 155.
228. Fachinetti, G.; Del Nero, S.; Floriani, C. J. Chem. Soc., Dalton Trans. 1976, 1046.
229. (a) Murray, J. G. J. Am. Chem. Soc. 1959, 81, 752.
230. (b) Murray, J. G. J. Am. Chem. Soc. 1961, 83, 1287.
231. Frerichs, S. R.; Stein, B. K.; Ellis, J. E. J. Am. Chem. Soc. 1987, 109, 5558.
232. Ellis, J. E.; Stein, B. K.; Frerichs, S. R. J. Am. Chem. Soc. 1993, 115, 4066.
233. Maher, J. M.; Beaty, R. P.; Cooper, N. J. Organometallics 1985, 4, 1354.
234. Datta, S.; Fischer, M. B.; Wreford, S. S. J. Organomet. Chem. 1980, 188, 353.
235. Whitesides, G. M.; Casey, C. P.; Krieger, C. J. Am. Chem. Soc. 1971, 93, 1379.
236. Blackburn, D. W.; Chi, K.-M.; Frerichs, S. R.; Tinkham, M. L.; Ellis, J. E. Angew. Chem., Int. Ed. Engl. 1988, 27, 437.
237. Cloke, F. G. N.; Lappert, M. F.; Lawless, G. A.; Swain, A. C. J. Chem. Soc., Chem. Commun. 1987, 1667.
238. Frerichs, S. R.; Ellis, J. E. J. Organomet. Chem. 1989, 359, C41.
239. Ellis, J. E.; DiMaio, A. J.; Rheingold, A. R.; Haggerty, B. S. J. Am. Chem. Soc. 1992, 114, 10676.
240. Soula, G. J. Org. Chem. 1985, 50, 3717. This inexpensive ionophore, available from Aldrich, is about as effective as 18-crown-6 for the complexation of a K cation.
241. Chi, K.-M.; Frerichs, S. R.; Philson, S. B.; Ellis, J. E. J. Am. Chem. Soc. 1988, 110, 303.
242. 2- in our laboratory.
243. Ellis, J. E.; Chi, K.-M. J. Am. Chem. Soc. 1990, 112, 6022.
244. Jilek, R. E.; Fischer, P. J.; Ellis, J. E. Inorg. Synth. 2006, submitted for publication.
245. Urnezius, E.; Brennessel, W. W.; Ellis, J. E. Abstracts of Papers; 221st National Meeting of the American Chemical Society, San Diego, CA, Apr 1-5, 2001; American Chemical Society: Washington, DC, 2001; INOR 650.
246. Urnezius, E.; Brennessel, W. W.; Cramer, C. J.; Ellis, J. E.; Schleyer, P. v. R. Science 2002, 295, 832.
247. Scott, N. D.; Walker, J. F. (to E. I. duPont de Nemours and Co.). U.S. Patent 2,177,412, Oct 24, 1939.
248. Chatt, J.; Davidson, N. J. Chem. Soc. 1965, 843.
249. Jonas, K. J. Organomet. Chem. 1974, 78, 273.
250. Scott, F.; Krüger, C.; Betz, P. J. Organomet. Chem. 1990, 387, 113.
251. (a) Albright, J. O.; Brown, L. D.; Datta, S.; Kouba, J. K.; Wreford, S. S.; Foxman, B. M. J. Am. Chem. Soc. 1977, 99, 5518.
252. (b) Albright, J. O.; Datta, S.; Dezube, B.; Kouba, J. K.; Marynick, D. S.; Wreford, S. S.; Foxman, B. M. J. Am. Chem. Soc. 1979, 101, 611.
253. (a) Hawker, P. N.; Kündig, E. P.; Timms, P. L. J. Chem. Soc., Chem. Commun. 1978, 730.
254. (b) Hawker, P. N.; Timms, P. L. J. Chem. Soc., Dalton Trans. 1983, 1123.
255. See: Reference 57, pp 343-345.
256. Kündig, E. P.; Timms, P. L. J. Chem. Soc., Dalton Trans. 1980, 991 and references cited therein.
257. Fischer, E. O.; Hafner, W. Z. Naturforsch. 1955, 10B, 665.
258. Cloke, F. G. N.; Green, M. L. H. J. Chem. Soc., Dalton Trans. 1981, 1938.
259. Calderazzo, F.; Pampaloni, G. J. Organomet. Chem. 1995, 500, 47. Calderazzo and Pampaloni have been key pioneers in the exploration of low-valent chemistry of the group 4 and 5 elements. This review provides a particularly cogent account of their remarkable progress in this area up to the early 1990s.
260. Pomije, M. K. Ph.D. Thesis, University of Minnesota, Minneapolis, MN, 1995.
261. Brennessel, W. W.; Ellis, J. E.; Pomije, M. K.; Sussman, V. J.; Urnezius, E.; Young, V. G., Jr. J. Am. Chem. Soc. 2002, 124, 10258.
262. Sussman, V. J.; Ellis, J. E. Unpublished results.
263. Brennessel, W. W.; Ellis, J. E.; Roush, S. N.; Strandberg, B. N.; Woisetschläger, O. E.; Young, V. G., Jr. Chem. Commun. 2002, 2356.
264. Fischer, E. O.; Elschenbroich, C.; Kreiter, C. G. J. Organomet. Chem. 1967, 7, 481.
265. Morand, P. D.; Francis, D. G. Organometallics 1985, 4, 1653.
266. Leach, P. A.; Geib, S. J.; Corella, J. A.; Warnock, G. F.; Cooper, N. J. J. Am. Chem. Soc. 1994, 116, 8566.
267. Seaburg, J. K.; Fischer, P. J.; Young, V. G., Jr.; Ellis, J. E. Angew. Chem., Int. Ed. Engl. 1998, 37, 155.
268. Elschenbroich, C.; Möckel, R.; Bilger, L. Z. Naturforsch 1984, 39B, 375. This substance was obtained by condensation of Cr atoms with excess anthracene and could not be freed from the latter without decomposition.
269. Klein, H.-F.; Ellrich, K.; Lamac, S.; Lull, G.; Zsolnai, L.; Huttner, G. Z. Naturforsch. 1985, 40B, 1377.
270. Brennessel, W. W.; Young, V. G., Jr.; Ellis, J. E. Angew. Chem., Int. Ed. 2002, 41, 1211.
271. Barybin, M. V.; Young, V. G., Jr.; Ellis, J. E. J. Am. Chem. Soc. 1999, 121, 9237.
272. Barybin, M. V.; Young, V. G., Jr.; Ellis, J. E. J. Am. Chem. Soc. 2000, 122, 4678.
273. Barybin, M. V. Personal communication.