Chem. Rev. 1996, 96, 877−910 877 Chemical Redox Agents for Organometallic Chemistry Neil G. Connelly*,† and William E. Geiger*,‡ School of Chemistry, University of Bristol, U.K., and Department of Chemistry, University of Vermont, Burlington, Vermont 05405-0125 Received October 3, 1995 (Revised Manuscript Received January 9, 1996) Contents I. Introduction 877 A. Scope of the Review 877 B. Benefits of Redox Agents: Comparison with 878 Electrochemical Methods 1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 The authors (Bill Geiger, left; Neil Connelly, right) have been at the forefront of organometallic electrochemistry for more than 20 years and have had 1. Radical Cations 891 a long-standing and fruitful collaboration. 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich 894 Neil Connelly took his B.Sc. (1966) and Ph.D. (1969, under the direction Compounds of Jon McCleverty) degrees at the University of Sheffield, U.K. Post- 4. Quinones 895 doctoral work at the Universities of Wisconsin (with Lawrence F. Dahl) 5. Other Organic Oxidants 896 and Cambridge (with Brian Johnson and Jack Lewis) was followed by an appointment at the University of Bristol (Lectureship, 1971; D.Sc. degree, III. Reductants 896 1973; Readership 1975). His research interests are centered on synthetic A. Inorganic 896 and structural studies of redox-active organometallic and coordination 1. Alkali Metals 896 complexes and have been presented in more than 150 publications. He is an active but unsuccessful orienteer and an optimistic but often 2. Complex Reducing Agents 898 disappointed supporter of Brentford Football Club. 3. Hydrazine 898 B. Organic 898 Bill Geiger received his B.S. from Canisius College (1965) and his Ph.D. 1. Metal Naphthalenides 898 from Cornell University (with David H. Geske, 1969) and did postdoctoral 2. Benzophenone Anion Radical 899 work at the University of California at Riverside with August H. Maki and 3. Triethylamine 900 at Northwestern University with Donald E. Smith before joining the faculty at Southern Illinois University in 1970. In 1974 he moved to the University 4. C2(NMe2)4 900 of Vermont. His main interest has been in the use of electrochemistry C. Organometallic 900 and spectroelectrochemistry to probe the molecular and electronic 1. Metal Sandwich Complexes 900 structures of odd-electron organometallic compounds. Born and raised 2. Metal Carbonylates 903 in Buffalo, he has been an avid fan of the Buffalo Bills since their inception, so he is familiar with near misses. IV. Conclusions 903 V. Appendix: Syntheses of Ferrocenium and 904 Diazonium Salts A. Ferrocenium Salts 904 I. Introduction 1. Method i. Ferrocenium Tetrafluoroborate, 904 [FeCp2][BF4] A. Scope of the Review 2. Method ii. Ferrocenium 904 As interest has grown in electron-transfer (ET) Hexafluorophosphate, [FeCp2][PF6] reactions of organometallic compounds, so too has the 3. Method iii. Acetylferrocenium 904 use of chemical oxidizing and reducing agents to Tetrafluoroborate, [Fe(η-C5H4COMe)Cp]- effect these transformations. The aim of this review [BF4] is to show how one-electron oxidants and reductants B. 4-Fluorobenzenediazonium 904 have been used in preparative chemistry (incorporat- Hexafluorophosphate, [N2C6H4F-4][PF6] ing both synthetic applications and generation of VI. List of Abbreviations 904 VII. Acknowledgments 904 † University of Bristol. VIII. References 904 ‡ University of Vermont. 0009-2665/96/0796-0877$25.00/0 © 1996 American Chemical Society + + 878 Chemical Reviews, 1996, Vol. 96, No. 2 Connelly and Geiger species for in situ characterization) in nonaqueous 1. Advantages of Chemical Redox Agents solutions, the usual media for organometallic ET reactions. It is hoped that the information in this a. Absence of Supporting Electrolyte. A post- review will also be useful to those interested in ET electrolysis solution contains a supporting electrolyte reactions of organic and inorganic systems, which salt in large (up to 1000-fold) excess over the desired have more often involved the use of labile metal ions electrode product. If the latter carries a charge, it such as M(III), M ) Fe, Tl1 (but see ref 2). may have a solubility similar to that of the support- ing electrolyte, making separation difficult. Perhaps A few words are in order about the reagents we the greatest advantage of chemical redox agents is have chosen to describe. Given the vast array of that the experimentalist is not confronted with this molecules and ions known to undergo one-electron separation problem in the workup of the reaction processes, some focus in coverage is necessary. We solution. have emphasized reagents in common usage and provide references to show typical applications rather b. Rapid, Large-Scale Preparations. Chemical than attempt comprehensive listings. We have also redox reactions generally yield larger quantities of included some less widely known reagents which are, products in briefer reaction times, and at higher in our opinion, worthy of further development. The concentrations, when compared with electrolytic subjective nature of such choices is obvious. Finally, preparations. Except for thin-layer electrochemical 7a,b we have not treated photochemically-generated cells, which are very limited in the quantities of reducing agents which, although generally transient reagent that can be produced, preparative electro- species, may have advantages in some applications.3 chemical cells have reaction times of tens of minutes, a time frame that may be troublesome if the desired The reader will note that in places we have referred product has limited stability. Homogeneous chemical to personal communications from colleagues. We are redox reactions, on the other hand, often proceed as grateful to them for providing many practical hints rapidly as solutions of the redox agent and the on the preparation and use of the particular reagents substrate are mixed. with which they are highly experienced. We would also appreciate correspondence from readers who use This time-scale advantage is compromised when other valuable oxidants or reductants which we may the chemical redox reaction is heterogeneous, as have inadvertently missed. occurs with dissolving-metal reductions, for example, or when the reagent is sparingly soluble, for example, B. Benefits of Redox Agents: Comparison with when ceric ammonium sulfate is used in CH2Cl2. The mass transfer factors which come into play are then Electrochemical Methods analogous to those encountered in electrolysis experi- Brief treatments have previously appeared con- ments. cerning applications of redox agents in metal dithio- Redox agents are easily adapted to low-temperature lene chemistry2a and in organic ET chemistry.2b In studies. Several applications are quoted below this section we emphasize the comparative benefits wherein the redox agent and the substrate are and shortcomings in chemical vs electrochemical allowed to dissolve and mix just above the melting approaches to preparative redox chemistry. point of a solvent, conditions very hard to duplicate Electrochemical methods are without rival for in practical electrochemical experiments. In elec- investigating the mechanisms of ET reactions.4 In trolysis experiments, lower diffusion coefficients and preparative applications, however, electrochemical higher ohmic effects lengthen reaction times at lower and nonelectrochemical approaches are closer in temperatures.7c relative merit. An experimental protocol making use c. Use of Nonpolar Solvents. The nature of the of the complementary aspects of both approaches is solvent medium influences the course of ET reactions. often more effective than either individual method. In electrochemistry, the use of solvents with polari- Controlled potential electrolysis (CPE) is the elec- ties significantly less than those of CH2Cl2 ( ) 9) trochemical method most often adopted for synthetic- and THF ( ) 7) is quite difficult because the scale redox reactions.4 Its versatility (wide range of electrolyte salt must dissolve and appreciably dis- accessible potentials) and precision ((1 mV or better sociate in order to render the solution conducting. in the absence of resistance effects) make CPE ideal Avoiding the requirement of a supporting electrolyte for forcing the uptake or release of one or more in chemical redox reactions opens opportunities for electrons from a substrate. the use of very low polarity solvents such as pentane The literature of CPE is well-developed for organic, and toluene in ET reactions. inorganic, and organometallic systems.5,6 When CPE Two potential major benefits arise from the use of is coupled with voltammetric methods such as cyclic low-polarity solvents such as aromatic and aliphatic voltammetry, polarography (in its various forms), and hydrocarbons, one relating to reactivity, the other to voltammetry at rotated electrodes, electrochemical solubility. Low-polarity solvents are often relatively methods can initiate and monitor the progress of noncoordinating and seldom displace ligands from simple or complex redox processes. Putting aside the primary redox product. For this reason, in- matters of availability of equipment and the inves- creased chemical stability may often be observed for tigator’s training