ABSTRACT
I. Introduction ........................................................................................................................ 1357 II.Electrochemical Synthesis of Organoelemental Compounds............................................. 1358
A.Oxidative Formation of Element-Carbon Bonds ....................................................... 1358 1.Oxidation of Organoelemental Compounds Using Reactive Anodes .................. 1358
B.Reductive Formation of Element-Carbon Bonds ....................................................... 1359 1.Reduction of Organic Compounds Using Reactive Cathodes ............................. 1359 2.Reduction of Organic Compounds in the Presence of Element Halides ............. 1360 3.Reduction of Organic Compounds Using Reactive Anodes of an Element......... 1363
III.Electrochemical Oxidation of Organoelemental Compounds ............................................ 1363 A.Electrochemical Oxidation of Group 1 and 2 Organoelemental Compounds ............ 1363 B.Electrochemical Oxidation of Group 13 Organoelemental Compounds .................... 1364 C.Electrochemical Oxidation of Group 14 Organoelemental Compounds .................... 1365
1.Electrochemical Oxidation of Tetraorganoelemental Compounds ...................... 1365 2.Electrochemical Oxidation of Dielemental Compounds (R3E-ER3) .................. 1376 3.Electrochemical Oxidation of Element-Element Double Bonds
(R2E═ER2,R2E═ER-ER═ER2) .......................................................................... 1377 4.Electrochemical Oxidation of Organoelemental Hydrides (R3EH) ..................... 1379 5.Electrochemical Oxidation of Stable Radicals of the Heavy Group 14
Elements (R3E .) ................................................................................................... 1379
6.Electrochemical Oxidation of Silylenes and Germylenes ((R2N)2E:) .................. 1380 7.Electrochemical Oxidation of Other Types of Group 14 Organoelemental
Compounds .......................................................................................................... 1380 IV.Electrochemical Reduction of Organoelemental Compounds ........................................... 1381
A.Electrochemical Reduction of Group 13 Organoelemental Compounds .................... 1382 B.Electrochemical Reduction of Group 14 Organoelement Halides .............................. 1382
1.Reduction Potentials and General Reaction Patterns of Group 14 Organoelement Halides ....................................................................................... 1382
2.Reductive Formation of Element-Element Bonds ............................................... 1383 3.Reductive Formation of Element-Carbon Bonds ................................................ 1385
C. ElectrochemicalReductionofGroup14OrganoelementalCompoundsContaining Reducible π-and σ-Systems........................................................................................ 1386
D.Electrochemical Reduction of Group 15 Organoelemental Compounds.................... 1386 References .................................................................................................................................... 1387
The electrochemistry of other organometallic compounds, especially transition metal compounds, is discussed in Chapter 36. This chapter will focus on the electrochemical synthesis and reactions of organic compounds containing main group elements. The electrochemistry of organoelemental compounds has a long history, and enormous advances have been made in the study of this šeld so far. The scope of this subject is, therefore, too extensive to be covered completely in a single chapter. There are excellent review articles on general electrochemistry of organoelemental compounds [1-9] and specišc topics [10-12] in this šeld. Thus, the approach here is to present those fundamental aspects of electrochemical synthesis and reactions of organoelemental compounds with special emphasis on recent developments. This chapter is not an exhaustive compilation of all known reactions, but rather sampling of sufšcient variety to illustrate the fascinating chemistry of electrochemical synthesis and reactions of organoelemental compounds.
