Organometallic electrochemistry: Origins, development, and future

Organometallics

Volumn 26, Issue 24, 2007, Pages 5738-5765

  Geiger, William E ^a  

^a UNIVERSITY OF VERMONT   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOMETALLIC ELECTROCHEMISTRY; ORGANOTRANSITION METAL COMPLEXES; ORGANOTRANSITION METALS;

ELECTROCHEMISTRY; ELECTRON TRANSITIONS; METAL COMPLEXES; MOLECULAR STRUCTURE; REACTION RATES; TRANSITION METALS;

ORGANOMETALLICS;

EID: 36749009541     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700558k     Document Type: Review

References (454)

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17. Ironically, one of the outstanding electrochemists of our time, Allen J. Bard, started his graduate studies in the Wilkinson group in September 1955. When Wilkinson, later honored for his work with the 1973 Nobel Prize in chemisitry, failed to get tenure and left Harvard in January, 1956, Bard joined the Lingane group.
18. Among the systems studied by Ralph (Buzz) Adams was dopamine, which was becoming known to be involved in neurological functions. Adams' goal of in vivo electrochemical studies of neurotransmitters has been realized by him and his students. For leading references to the important and rapidly developing area of analytical neuroelectrochemistry see: Venton, B. J.; Michael, D. J.; Wightman, R. M. J. Neurochem. 2003, 84, 373.
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44. The discovery and development of bis(arene)chromium chemistry has been the subject of earlier reviews in this Journal. See: Seyferth, D. Organometallics 2002, 21, 2800.
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60. 4] in dimethoxyethane) for which the potential of ferrocene has not, to our knowledge, been reported. By inspection of several potentials reported in refs 35 and 36 compared to those measured in our own laboratory, I estimate that addition of approximately +0.2 V converts the reported potentials to the ferrocene/ferrocenium reference potential.
61. Dessy's contacts included Howard Malmstadt (University of Illinois), Chris Enke (Princeton University), and Fred Anson and Bob Osteryoung (Cal Tech).
62. Dessy, R. E.; Pohl, R. L. J. Am. Chem. Soc. 1968, 90, 1995.
63. Dessy, R. E.; Kornmann, R.; Smith, C.; Haytor, R. J. Am. Chem. Soc. 1968, 90, 2001.
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65. Dessy, R. E.; Wieczorek, L. J. Am. Chem. Soc. 1969, 91, 4963.
66. (a) Dessy, R. E.; Charkoudian, J. C.; Abeles, T. P.; Rheingold, A. L. J. Am. Chem. Soc. 1970, 92, 3947.
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68. (c) Dessy, R. E.; Rheingold, A. L.; Howard, G. D. J. Am. Chem. Soc. 1972, 94, 746.
69. (d) Dessy, R. E.; Bares, L. Acc. Chem. Res. 1972, 5, 415. One anecdote of this period involves the work of Arnold Rheingold, who was beginning a postdoc with Dessy after receiving his Ph.D. from the University of Maryland in 1970. He was assigned the task of obtaining NMR spectra of diamagnetic charged species being generated electrochemically. Expanding and being strapped for space, the Dessy group appropriated a room that was being used only periodically and moved its 100 MHz NMR spectrometer into it. Arnie Rheingold recorded his spectra in this converted men's room.
70. Gutmann, V.; Schöber, G. Monatsh. Chem. 1957, 88, 206.
71. Vlček, A. A. Collect. Czech. Chem. Commun. 1965, 30, 952.
72. Mǎsek, J. Collect. Czech. Chem. Commun. 1965, 30, 4117.
73. Denisovich, L. I.; Gubin, S. P.; Chapovski Yu, A.; Ustynok, N. A. Bull. Acad. Sci. USSR, Div. Chem. Sci. 1968, 891.
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88. Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706.
89. The now widely used lettering system E and C refers to an electron-transfer process as E and a chemical reaction as C. Structural changes that are not concomitant with electron transfer are included in the latter.
90. Gunasingham, H. In Electrochemistry, Past and Present; Stock, J. T., Orna, M. V., Eds.; ACS Symposium Series; American Chemical Society: Washington, DC, 1989; Vol. 390, Chapter 17.
91. The first commercial potentiostat used in my lab was the PAR 173, to which a waveform generator was interfaced to scan potentials. This unit, purchased in early 1971, is still used in our lab for spectroelectrochemical experiments, having required only the replacement of two switches during its lifetime.
92. 4 drawing is used to symbolize a square-planar complex having two dithiolate ligands. Other stoichiometries were also observed.
93. Reviews of the early metal dithiolene work may be found in: (a) McCleverty, J. A. In Progress in Inorganic Chemistry; Cotton, F. A., Ed.; John Wiley and Sons: New York, 1968; Vol. 10, p 49.
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100. (b) Pierpont, C. G.; Lange, C. W. In Progress in Inorganic Chemistry; Karlin, K. D., Ed.; 1994; Vol. 41, p 331.
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102. (d) Andrea, R. R.; de Lange, W. G. J.; van der Graaf, T.; Rijkhoff, M.; Stufkens, D. J.; Oskam, A. Organometallics 1988, 7, 1100.
103. (e) Hirao, T. Coord. Chem. Rev. 2002, 226, 81.
104. (f) Ray, K.; Weyhermüller, T.; Goossens, A.; Crajé, M. W. J.; Wieghardt, K. Inorg. Chem. 2003, 42, 4082.
105. (g) Kaim, W. J. Chem. Soc., Dalton Trans. 2003, 761
106. (h) Dei, A.; Gatteschi, D.; Sangregorio, C.; Sorace, L. Acc. Chem. Res. 2004, 37, 827.
107. (i) Chlopek, K.; Bill, E.; Weyhermüller, T.; Wieghardt, K. Inorg. Chem. 2005, 44, 7087.
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110. For a review of this early metal carborane work see: Callahan, K. P.; Hawthorne, M. F. Adv. Organomet. Chem. 1976, 14, 145.
111. O'Neill, M. E.; Wade, K. In Metal Interactions with Boron Clusters; Grimes, R. N., Ed.; Plenum Press: New York, 1982; Chapter 1.
112. Hawthorne, M. F.; Young, D. C.; Wegner, P. A. J. Am. Chem. Soc. 1965, 57, 1818.
113. A 1982 review of the electrochemistry of metalloboranes and -carboranes contained exhaustive coverage of the Hawthorne group results to that date. See: Geiger, W. E. In Metal Interactions with Boron Clusters; Grimes, R. N., Ed.; Plenum Press: New York, 1982; Chapter 6.
114. Geiger, W. E.; Smith, D. E. J. Chem. Soc., Chem. Commun. 1971, 8. Hawthorne's group supplied the metal dicarbollides studied in this work. For a report of their electron-transfer kinetics
115. see: Geiger, W. E.; Smith, D. E. J. Electroanal. Chem. 1974, 50, 31.
116. Warren, L. F., Jr.; Hawthorne, M. F. J. Am. Chem. Soc. 1970, 92, 1157.
117. Paxson, T. E.; Kaloustian, M. K.; Tom, G. M.; Wiersema, R. J.; Hawthorne, M. F. J. Am. Chem. Soc. 1972, 94, 4882. Note that the systems studied in this paper were a modification of the parent system in that the two CMe groups shown in Figure 6 are replaced by a bridging trimethylene group.
118. The time required for virtually complete (>99%) bulk electrolysis is a function of diffusion coefficient of the analyte at a given temperature, physical aspects of the electrolysis cell (especially the ratio of working electrode area to solution volume), and mechanical aspects of mass transfer such as stirring efficiency. For an excellent treatment of these and other experimental factors see: Bard, A. J.; Santhanam, K. S. V. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1970; Vol. 4, pp 215 ff.
119. Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877.
120. The same cannot be said for the organic literature, which has a long history of using bulk electrolysis for synthetic-level preparations. Whereas the discrepancy in development of these two subdisciplines is due to a number of factors, it is worth noting that a high percentage of isolated organic electrolysis products are uncharged, making them easy to separate from the supporting electrolyte. For comprehensive treatments of organic electrochemistry see: (a) Steckhan, E., ed. Topics in Current Chemistry; Springer-Verlag: Berlin, 1987; Vol. 142.
121. (b) Fry, A. J. Synthetic Organic Electrochemistry, 2nd ed.; Wiley: New York, 1989.
122. (c) Lund, H.; Hammerich, O. Organic Electrochemistry, 4th ed.; Marcel Dekker: New York, 2001.
123. (d) Shono, T. Electroorganic Synthesis; Academic Press: London, 1991.
124. (e) Schäfer, H. J. In Encyclopedia of Electrochemistry; Bard, A. J., Stratmann, M., Eds.; Wiley-VCH: Weinheim, 2004; Vol. 8.
125. To convert to the ferrocene reference potential, 0.4 V has been subtracted from the potentials vs SCE reported in ref 67.
126. (a) Connelly, N. G.; Dahl, L. F. J. Am. Chem. Soc. 1970, 92, 7470.
127. (b) Connelly, N. G.; Dahl, L. F. J. Am. Chem. Soc. 1970, 92, 7472.
128. Connelly, N. G.; Johnson, G. A. J. Organomet. Chem. 1974, 77, 341.
129. Connelly, N. G. Chem. Soc. Rev. 1989, 18, 153.
130. (a) Baker, P. K.; Connelly, N. G.; Jones, B. M. R.; Maher, J. P.; Somers, K. R. J. Chem. Soc., Dalton Trans. 1980, 579.
131. (b) Baker, P. K.; Broadley, K.; Connelly, N. G. J. Chem. Soc., Dalton Trans. 1982, 471.
132. (a) Gulick, W. M., Jr.; Geiger, W. E.; Geske, D. H. J. Am. Chem. Soc. 1968, 90, 4218.
133. (b) Geiger, W. E.; Gulick, W. M., Jr. J. Am. Chem. Soc. 1969, 91, 4657.
134. In the spring of this tumultuous academic year, protests against the Vietnam war reached their apex at American colleges and universities. Owing to campus and political pressures, support of fundamental academic research by defense agencies, which included Allred's grant funding my work on organogermanium radical ions, disappeared almost overnight. As I recall, the chemistry building at Northwestern was closed for some days in response to those same pressures. The chemistry students and faculty expressed themselves through speeches and arguments on the steps of the building regarding less the war than the ethics of militarily funded fundamental academic research. Northwestern was just one of many universities that were severely affected. The Kent State shootings occurred on May 4, 1970.
135. Huebert, B. J.; Smith, D. E. J. Electroanal. Chem. 1971, 31, 333.
136. For later work on the reduction of cyclooctatetraene see: Petersen, R. A.; Evans, D. H. J. Electroanal. Chem. 1987, 222, 129.
137. Before moving to the University of Vermont in 1974, I held an Assistant Professor position at Southern Illinois University at Carbondale. The trianions shown in Figure 4 were based on our metal dithiolene work. See: (a) Mines, T. E.; Geiger, W. E. Inorg. Chem. 1973, 12, 1189.
138. 2- recorded at Columbia and noted that, indeed, there was a one-electron reduction wave close to cathodic electrolyte breakdown that had not been reported in their papers. Besides simply extending the metal dithiolene electron-transfer series, the Mines and Senftleber results established that more traditional metal-localized redox processes were also possible in these systems once the ligand orbitais that had given rise to their noninnocence had been filled. These papers described genuine Ni(I) complexes.
139. Geiger, W. E. J. Am. Chem. Soc. 1974, 96, 2632.
140. 89
141. El Murr, N.; Dabard, R.; Laviron, E. J. Organomet. Chem. 1973, 47, C13.
142. Holloway, J. D. L.; Bowden, W. L.; Geiger, W. E. J. Am. Chem. Soc. 1977, 99, 7089.
143. For a review of activity in this area see: Strelets, V. V. Coord. Chem. Rev. 1992, 114, 1.
144. Holloway, J. D. L.; Senftleber, F. C.; Geiger, W. E. Anal. Chem. 1978, 50, 1010.
145. Johnson, M. D. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergammon Press: Oxford, 1982; Vol. 4, p 479.
146. Marcus, R. A.; Eyring, H. Annu. Rev. Phys. Chem. 1964, 15, 155.
147. Hale, J. M. In Reactions of Molecules at Electrodes; Hush, N. S., Ed.; Wiley-Interscience: New York, 1971; pp 229 ff.
148. Reliable values for the heterogeneous charge-transfer rates of metallocenes were first obtained by ac polarography. The first broad study of heterogeneous e.t. rates of metal sandwich systems was done in the late Michael Weaver's lab at Purdue. See: (a) Weaver, M. J.; Gennett, T. Chem. Phys. Lett. 1985, 113, 213.
149. (b) Gennett, T.; Weaver, M. J. J. Electroanal. Chem. 1985, 186, 179.
150. (a) Laviron, E.; Roullier, L. J. Electroanal. Chem. 1985, 186, 1, and references therein.
151. (b) Evans, D. H.; O'Connell, K. M. In Electroanalytical Chemistry; Bard, A. J., Ed.; Marcel Dekker: New York, 1988; Vol. 14, pp 113 ff,
152. Rieger, P. H. Electrochemistry 2nd ed.;, Chapman and Hall: New York, 1994; p 264.
153. Geiger, W. E. In Progress in Inorganic Chemistry; Lippard, S. J., Ed.; John Wiley & Sons: New York, 1985; Vol. 33, pp 275-352.
154. (a) Fischer, E. O.; Elschenbroich, Ch. Chem. Ber. 1970, 103, 162.
155. (b) Huttner, G.; Lange, S. Acta Crystallogr. 1972, B28, 2049.
156. A later NMR study determined the activation barrier of the fluxional process: Darensbourg, M. Y.; Muetterties, E. L. J. Am. Chem. Soc. 1979, 100, 7425.
157. (a) Rieke, R. D.; Arney, J. S.; Rich, W. E.; Willeford, B. R., Jr.; Poliner, B. S. J. Am. Chem. Soc. 1975, 97, 5951.
158. (b) See also: Rieke, R. D.; Henry, W. P.; Arney, J. S. Inorg. Chem. 1987, 26, 420. In this work, the arene hapticity change was postulated to occur at the one-electron stage, but the experimental evidence was ambiguous.
159. See: Deganello, G. Transition Metal Complexes of Cyclic Polyolefins; Academic Press: London, 1979; Chapter II.
160. 4-COT) with potassium, followed by addition of water. The CV curves for this system were not published in the original paper, but appeared later in ref 101, p 223.
161. We also considered the possible presence of an impurity, especially because we were not very confident in our synthetic abilities at the time. Proper Schlenck techniques were not introduced into our lab until after my sabbatical leave in Richard Schrock's group at MIT in 1979.
162. (a) Fritz, H. P.; Keller, H. Z. Naturforch. 1961, 16B, 348.
163. (b) Fritz, H. P.; Keller, H. Chem. Ber. 1962, 95, 158.
164. Nakamura, A.; Hagihara, N. Bull. Chem. Soc. Jpn. 1960, 33, 425.
165. Otsuka, S.; Nakamura, A. Inorg. Chem. 1966, 5, 2059.
166. Although the singlets of the chair isomer at δ= 5.1 (fluxional COT ring) and 4.7 (Cp) were easily visible even in the old 60 MHz instruments, their presence was not discussed in the literature. Even the temperature-dependent NMR study of ref 106 did not identify the 1,3-isomer. After the publication of our communication on this system, the author received several notes from individuals who had worked on CoCp(COT) and had wondered what the "persistent impurity" was. We had the advantage of seeing from CV scans that the minor (ca 20%) and major species in solution gave electrochemically identical monoanions.
167. Moraczewski, J.; Geiger, W. E. J. Am. Chem. Soc. 1979, 101, 3407.
168. Moraczewski, J.; Geiger, W. E. J. Am. Chem. Soc. 1981, 103, 4779.
169. Albright, T. A.; Geiger, W. E.; Moraczewski, J.; Tulyathan, B. J. Am. Chem. Soc. 1981, 103, 4787.
170. The definitive analysis of the ESR data was done by Phil Rieger and published as part of a larger paper on the reductions of cobalt and nickel-group-COT complexes: Geiger, W. E.; Rieger, P. H.; Corbato, C.; Edwin, J.; Fonseca, E.; Lane, G. A.; Mevs, J. M. J. Am. Chem. Soc. 1993, 115, 2314.
171. Geiger, W. E.; Gennett, T.; Grzeszczuk, M.; Lane, G. A.; Moraczewski, J.; Salzer, A.; Smith, D. E. J. Am. Chem. Soc. 1988, 108, 7454.
172. (a) Geiger, W. E. Acc. Chem. Res. 1995, 28, 351.
173. (b) Tyler, D. R. Acc. Chem. Res. 1991, 24, 325.
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453. The great majority of dc polarograms were recorded by scanning to more negative potentials using strip-chart recorders. This gave a plot in which cathodic currents were "up" and negative potentials increased left to right.
454. Much less desirable is the CV recorded after the triangular sweep has been repeated one or more times without stopping at the rest potential. Under the scan rates often employed for routine CV scans, such scans have an approximately "steady state" behavior, which may be misleading.