Compounds bioinorganic

Misra, S.N., Gagnani, M.A., Devi, I, and Shukla, R.S. (2004) Biological and clinical aspects of lanthanide coordination compounds. Bioinorganic Chemistry and Applications, 2, 155-192. 

I have designed this eourse to be a general introduction to the study of inorganic chemistry proper. This comprises the chemistry of the elements and various special topics - organometallic compounds, bioinorganic chemistry, solid-state chemistry, solution chemistry, and others. For some topics, you will need additional backgroimd material, but you should get most of this from courses in the other branches of chemistry, including theoretical chemistry. 

There is a growing interest in modeling transition metals because of its applicability to catalysts, bioinorganics, materials science, and traditional inorganic chemistry. Unfortunately, transition metals tend to be extremely difficult to model. This is so because of a number of effects that are important to correctly describing these compounds. The problem is compounded by the fact that the majority of computational methods have been created, tested, and optimized for organic molecules. Some of the techniques that work well for organics perform poorly for more technically difficult transition metal systems. 

The effect of gold compounds on human neutrophil myeloperoxidase, in Bioinorganic Chemistry of Gold Coordination Compounds (eds B.M. Sutton and R.G. Franz), SK F, Philadelphia, pp. 58-66. 

After a consideration of optical transitions in which MMCT plays a role, and after a characterization of the excited states involved, a short review of mixed-valence compounds and their spectroscopy is in order. For more extended reviews we refer to Refs. [60,97], At least 40 elements of the periodic table form mixed-valence species which are of importance in solid state physics and chemistry, inorganic chemistry, materials science, geology and bioinorganic chemistry. It is usually their colors which are their most striking property (see also above), but they have more intriguing properties, for example electrical and magnetic properties. 

The first Ni Mossbauer spectrum of nickel in a bioinorganic compound with determinable EFG and isomer shift was reported for a nickel complex compound with planar [NiSJ core and considered as a model compound for hydrogenase. This Mossbauer spectrum from the formal Ni compound is presented in Fig. 7.16. The observed quadrupolar interaction can be understood in terms of ligand field theory. In this approach, the b g and levels (d y2 and d ) are not occupied which is expected to cause a large negative EFG contribution [32]. 

Pickett, C. J. Azametallic Electrochemistry. In Molecular Electrochemistry of Inorganic, Bioinorganic and Organo-metallic Compounds Pombeiro, A. J. L. McCleverty, J. A.Eds., NATO ASI Series C 1993, 385, 357-380. 

Table 3.4 lists values for A Eq and for some important oxidation and spin states found in bioinorganic molecules. Data are taken from reference 24 and from Table 1 of reference 25 for hemoglobin, myoglobin, and the picket-fence porphyrin model compound, FeTpivPP(l-Melm).25 The myoglobin and hemoglobin model compounds are discussed in Section 4.8.2. Reference 26 provides the Table 3.4 data on iron sulfur clusters found in many bioinorganic species.26 The unusual iron-sulfur and iron-molybdenum-sulfur clusters found in the enzyme nitrogenase are discussed more fully below and in Chapter 6. 

Chemists considering the design of model compounds for bioinorganic systems usually take one of two approaches ... 

Introduce instrumental techniques used in analysis of the bioinorganic systems I will lecture on (Chapter 3 Instrumental and Computer-Based Methods). Typically, these would be electron paramagnetic resonance (EPR) and Mossbauer spectroscopies not often covered in undergraduate instrumental analysis courses plus X-ray diffraction and NMR techniques used for structural analyses of metalloproteins and their small molecule model compounds. 

Kenneth Suslick has written several pertinent statements about the study of metalloproteins and their model compounds. This paradigm will guide the study of the varied bioinorganic systems described in this chapter. Additions to Suslick s statement in point 2 stress the importance of modern structural analysis (X-ray crystallography, EXAFS, EPR, and two- and three-dimensional high-held NMR) of the purihed metalloproteins and their model compounds. As paraphrased from reference 19, the following statements outline the steps involved in the study of metalloproteins ... 

This article presents the principles known so far for the synthesis of metal complexes containing stable carbenes, including the preparation of the relevant carbene precursors. The use of some of these compounds in transition-metal-catalyzed reactions is discussed mainly for ruthenium-catalyzed olefin metathesis and palladium-Znickel-catalyzed coupling reactions of aryl halides, but other reactions will be touched upon as well. Chapters about the properties of metal- carbene complexes, their applications in materials science and medicinal chemistry, and their role in bioinorganic chemistry round the survey off. The focus of this review is on ZV-heterocyclic carbenes, in the following abbreviated as NHC and NHCs, respectively. 

Metal complexes of stable carbenes—or more precisely metal complexes of car-benes that are now known to be stable—have developed from laboratory curiosities to widely used compounds. The basis for this development was laid by Wanzlick s and Ofele s discoveries in the 1960s, the recent revival has certainly been driven by Arduengo s first isolation of an A-heterocyclic carbene in 1991, and the result is a permanently increasing number of synthetic routes towards precursors for stable carbenes, towards stable carbenes themselves, and their metal complexes. Simultaneously with their accessibility, the applicability of these compounds to various fields such as homogeneous catalysis, materials science, medicinal and bioinorganic chemistry has been evaluated. 

---