Fundamental inorganic

Dance, I. (1998) Understanding structure and reactivity of new fundamental inorganic molecules metal sulfides, metallcarbohedranes, and nitrogenase, Chem. Commun. 523-530. 

The examples in this chapter represent only a fraction of the extensive synthetic chemistry inspired by the nitrogenase clusters, but they clearly illustrate contributions, deliberate and serendipitous, obtained from speculative synthetic analogue study. Nitrogenase has long served as an inspiration for creative studies in fundamental inorganic chemistry, and it will certainly continue in this role for the foreseeable future. 

Some fundamental inorganic chenustry that is important for understanding which complexes will undergo the aromatic C—and C—O bond-forming processes will be presented before the catalytic transformations. First, the three reaction types involved in the catalytic cycle to form arylanunes are similar to those found in the catalytic cycle for C—C bond formation oxidative addition of aryl halide to Pd(0) complexes, transmetallation that converts an arylpalladium halide complex to an arylpaUadium amido complex, and reductive elimination to form a C—or C—O bond. The oxidative addition step is identical to the addition that initiates C—C bond-fomting cross-couplings,f f but the steps that form the arylpalladium amido complexes and that produce the arylamine product are different. The mechanism for these steps is discussed after presentation of the scope of the amination process. 

The diverse collection of boron-nitrogen polymer chemistry summarized here points out that efforts in this area are fruitful and worthy of continuing attention. Furthermore, the considerable progress made in processing some of the polymers into useful ceramic compositions and forms demonstrates that fundamental inorganic polymer chemistry has practical and, perhaps in the near future, commercial utility. 

Luminescence has been used in conjunction with flow cells to detect electro-generated intennediates downstream of the electrode. The teclmique lends itself especially to the investigation of photoelectrochemical processes, since it can yield mfonnation about excited states of reactive species and their lifetimes. It has become an attractive detection method for various organic and inorganic compounds, and highly sensitive assays for several clinically important analytes such as oxalate, NADH, amino acids and various aliphatic and cyclic amines have been developed. It has also found use in microelectrode fundamental studies in low-dielectric-constant organic solvents. 

A challenging task in material science as well as in pharmaceutical research is to custom tailor a compound s properties. George S. Hammond stated that the most fundamental and lasting objective of synthesis is not production of new compounds, but production of properties (Norris Award Lecture, 1968). The molecular structure of an organic or inorganic compound determines its properties. Nevertheless, methods for the direct prediction of a compound s properties based on its molecular structure are usually not available (Figure 8-1). Therefore, the establishment of Quantitative Structure-Property Relationships (QSPRs) and Quantitative Structure-Activity Relationships (QSARs) uses an indirect approach in order to tackle this problem. In the first step, numerical descriptors encoding information about the molecular structure are calculated for a set of compounds. Secondly, statistical and artificial neural network models are used to predict the property or activity of interest based on these descriptors or a suitable subset. 

Inorganic Materials. Sol—gel chemistry involves first the formation of a sol, which is a suspension of soHd particles in a Hquid, then of a gel, which is a diphasic material with a soHd encapsulating a solvent. A detailed description of the fundamental chemistry is available in the Hterature (2—4). The chemistry involving the most commonly used precursors, the alkoxides (M(OR) ), can be described in terms of two classes of reactions ... 

Chlorine and Bromine Oxidizing Compounds. The organo chlorine compounds shown in Table 6 share chemistry with inorganic compounds, such as chlorine/77< 2-3 (9-j5y and sodium hypochlorite/7 )< /-j5 2-5 7. The fundamental action of chlorine compounds involves hydrolysis to hypochlorous acid (see Cm ORiNE oxygen acids and salts). 

The scientific interests of Anatoly K. Babko ranged widely, especially in regard to fundamental aspects of analytical chemistry, applications of organic reagents in inorganic analysis, chemistry of complex compounds (including heteropolyacids), analytical applications of complex compounds in photometry, luminescence and chemiluminescence, ion chromatography, and liquid-liquid extraction. 

Barnett, J., and Malati, M.A. (1997J Fundamentals of Inorganic Chemistry, Horwood Publishing, Chichester. 

The extent to which one ion is absorbed in preference to another is of fundamental importance it will determine the readiness with which two or more substances, which form ions of like charge, can be separated by ion exchange and also the ease with which the ions can subsequently be removed from the resin. The factors determining the distribution of inorganic ions between an ion exchange resin and a solution include ... 

There are three types of electron transfers, firstly the generation of an electron electrochemically, by y-irradiation, or by photolytic dissociation, secondly the transfer of an electron from an inorganic or organic compound, referred to as a nucleophilic homolytic leaving group (Zollinger, 1973 a), and thirdly a transfer from a transition metal or transition metal ion complex. In this section we will discuss the fundamental aspects of these three types. In the following sections and in Chapter 10, specific examples and synthetic applications will be summarized. 

Chelates in inorganic polarographic analysis fundamentals. M. Kapanica, J. Dolezal and J. Zyka, Chelates Anal. Chem., 1967, 1, 145-177 (113). 

---