Main group chemistry and

Recently, Mark J. Fink joined us as Editor. His perspective on main group chemistry and the interface with transition metal chemistry and applications ideally places him to maintain the synergy between main group and transition metal organometallic chemistry that Advances in Organometallic Chemistry has endeavored to chronicle. 

Table 7.3 Suggested simple compounds and complexes to illustrate a Features of Interest approach to (a) main group chemistry and (b) transition metal chemistry.

Quantum-Chemical Methods in Main-Group Chemistry Thomas M. Klapotke and Axel Schulz Published 1998, ISBN 0 471 97242 8... 

This fundamental discovery dramatically affected the whole chemistry of main-group elements. Subsequently, a series of new compounds with silicon element multiple bonds has been introduced. Within only a few years, stable silenes (silaethenes with a Si = C double bond) [8-11], silaimines Si = N [12-14], and silaphosphenes Si = P [15] were synthesized. As a pacemaker, silicon chemistry has exerted a strong influence on further areas of main-group chemistry a variety of stable molecules with Ge = Ge [16], P = P [17], As = As [18], P = C and P = C [19-22] bonds were subsequently isolated, and systems with cumulated double bonds P = C = P [23-25] are also known today. 

Annual reviews of both transition element and main group chemistry are now published periodically in Coord. Chem. Rev. and the details of those which have appeared to date are given below. 

Gielen, M. Willem, R. In Kumar Das, V. G. (Ed.), Main Group Elements and Their Compounds Perspectives in Materials Science, Chemistry and Biology, Springer/Narosa, Berlin, 1996 p. 446. 

The reaction between a Lewis acid R3M and a Lewis base ER3, usually resulting in the formation of a Lewis acid-base adduct R3M—ER3, is of fundamental interest in main group chemistry. Numerous experiments, in particular reactions of alane and gallane MH3 with amines and phosphines ER3, have been performed [14]. Several general coordination modes, as summarized in Fig. 2, have been identified by X-ray diffraction. 

With the exception of a brief report of a dimethylaluminum complex [5], the coordination chemistry of the monomeric anion in (4) has not been investigated. By contrast, Stahl and co-workers have carried out extensive studies of both main group element and transition-metal complexes of the chelating dianion in the cube (7), which have been summarized in a recent review [9]. A noteworthy feature of the ligand behaviour of this N,N chelating dianion is the additional in-... 

Abstract This chapter is devoted to phosphinous amides, a particular class of tervalent aminophosphanes. First, attention is focused on their stability and synthetic procedures. Reports dealing with their prototropic equilibrium and main group chemistry are also considered. Last but not least the really important applications of these species as metal ligands in the field of catalysis are reviewed, including asymmetric variants. 

N. Pelloux-Leon and Y. Vallee, Main Group Chemistry News, 1994, 2, 22. 

In recent years, the amount of research time devoted to materials chemistry has risen almost exponentially and sulfur-based radicals, such as the charge-transfer salts based upon TTF (tetrathiafulvalene), have played an important role in these developments. These TTF derivatives will not be discussed here but are dealt with elsewhere in this book. Instead we focus on recent developments in the area of group 15/16 free radicals. Up until the latter end of the last century, these radicals posed fundamental questions regarding the structure and bonding in main group chemistry. Now, in many cases, their thermodynamic and kinetic stability allows them to be used in the construction of molecular magnets and conductors. In this overview we will focus on the synthesis and characterisation of these radicals with a particular emphasis on their physical properties. 

Tertiary stibines, R3Sb, are the most frequently used antimony ligands and the coordination chemistry of these donors to transition metals of the groups 3-12 and also to main group 13 and 15 elements has been reviewed several times, often together with other pnicogen ligands.1,2,6-8... 

Fundamentally, the high nucleophilicity of stable carbenes, coupled with the tendency to increase the coordination number at the carbenic carbon, renders their chemical behavior very similar to that of electron-rich phosphines. As such, they have aroused considerable interest as ligands in p-, cl-, and / -block chemistry. Earlier reviews (7a,b) have covered some aspects of the main group chemistry of stable nucleophilic carbenes however, there has been considerable recent activity in this field, and thus a comprehensive, up-to-date review was considered desirable. 

Dr. Engel is a member of the American Chemical Society, the International Council on Main Group Chemistry (currently executive secretary), the New York Academy of Sciences, Sigma Xi, and the Royal Society of Chemistry. He has published over 120 articles and more than 60 meeting presentations. 

From the localized Lewis-like perspective, we can picture coordinative metal-ligand interactions as involving two distinct types of localized bonding (which have already been discussed in the context of main-group chemistry Sections 3.2.11 and 3.5) ... 

Although formally a transition metal the structural chemistry of mercury as a group 12 element in amalgams shows typical features close to those of main group 13 and 14 metals. 

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