Inorganic chemistry complexes

At Preparative inorganic chemistry. Complex compounds. Organo-metallic compounds... 

Surfactants have also been of interest for their ability to support reactions in normally inhospitable environments. Reactions such as hydrolysis, aminolysis, solvolysis, and, in inorganic chemistry, of aquation of complex ions, may be retarded, accelerated, or differently sensitive to catalysts relative to the behavior in ordinary solutions (see Refs. 205 and 206 for reviews). The acid-base chemistry in micellar solutions has been investigated by Drummond and co-workers [207]. A useful model has been the pseudophase model [206-209] in which reactants are either in solution or solubilized in micelles and partition between the two as though two distinct phases were involved. In inverse micelles in nonpolar media, water is concentrated in the micellar core and reactions in the micelle may be greatly accelerated [206, 210]. The confining environment of a solubilized reactant may lead to stereochemical consequences as in photodimerization reactions in micelles [211] or vesicles [212] or in the generation of radical pairs [213]. 

DFT calculations offer a good compromise between speed and accuracy. They are well suited for problem molecules such as transition metal complexes. This feature has revolutionized computational inorganic chemistry. DFT often underestimates activation energies and many functionals reproduce hydrogen bonds poorly. Weak van der Waals interactions (dispersion) are not reproduced by DFT a weakness that is shared with current semi-empirical MO techniques. 

Rappe A K, K S Colwell and C J Casewit 1993. Application of a Universal Force Field to Metal Complexes. Inorganic Chemistry 32 3438-3450. 

For organometailic compounds, the situation becomes even more complicated because the presence of elements such as platinum, iron, and copper introduces more complex isotopic patterns. In a very general sense, for inorganic chemistry, as atomic number increases, the number of isotopes occurring naturally for any one element can increase considerably. An element of small atomic number, lithium, has only two natural isotopes, but tin has ten, xenon has nine, and mercury has seven isotopes. This general phenomenon should be approached with caution because, for example, yttrium of atomic mass 89 is monoisotopic, and iridium has just two natural isotopes at masses 191 and 193. Nevertheless, the occurrence and variation in patterns of multi-isotopic elements often make their mass spectrometric identification easy, as depicted for the cases of dimethylmercury and dimethylplatinum in Figure 47.4. 

B. Jensen, Phase and Structure determination of a New Complex Alkali Aluminum Fluoride, Institute of Inorganic Chemistry, Norwegian Technical University, Trandheim, 1969. 

G. D. James, Rec. Chem. Prog. 31, 199 (1970). Inorganic chemistry of complex hydrides. 

C. A. McAuliffe and W. Levason, Studies in Inorganic Chemistry, Vol. 1, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, The Netherlands, 1979. 

When a Br nsted base functions catalytically by sharing an electron pair with a proton, it is acting as a general base catalyst, but when it shares the electron with an atom other than the proton it is (by definition) acting as a nucleophile. This other atom (electrophilic site) is usually carbon, but in organic chemistry it might also be, for example, phosphorus or silicon, whereas in inorganic chemistry it could be the central metal ion in a coordination complex. Here we consider nucleophilic reactions at unsaturated carbon, primarily at carbonyl carbon. Nucleophilic reactions of carboxylic acid derivatives have been well studied. These acyl transfer reactions can be represented by... 

It has been argued that the inorganic chemistry of boron is more diverse and complex than that of any other element in the periodic table. Indeed, it is only during the last three decades that the enormous range of structural types has begun to... 

F. Wells, Structural Inorganic Chemistry, 5th edn., Oxford University Press, Oxford, 1984 Chap. 12, Binary metal oxides, pp. 531-74 Chap. 13, Complex. oxides, pp. 575-625. 

This chapter is devoted to complex ions and the important role they play in inorganic chemistry. We consider in turn—... 

The basic ideas concerning the structure and geometry of complex ions presented in this chapter were developed by one of the most gifted individuals in the history of inorganic chemistry,... 

Platinum ammine complexes have been a fertile area for studying transinfluence. Table 3.21 lists data for a range of ammines showing how /(195Pt-15N) depends upon the trans-atom [153]. (A further selection of data can be found in R.V. Parish, NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, Ellis-Horwood, Chichester, 1991, pp. 76, 87.) Possibly the most detailed study (of complexes of tribenzylphosphine) examined over a hundred neutral and cationic complexes [154] (Table 3.22). 

The structure theory of inorganic chemistry may be said to have been bom only fifty years ago, when Werner, Nobel Laureate in Chemistry in 1913, found that the chemical composition and properties of complex inorganic substances could be explained by assuming that metal atoms often coordinate about themselves a number of atoms different from their valence, usually four atoms at the comers either of a tetrahedron or of a square coplanar with the central atom, or six atoms at the comers of an octahedron. His ideas about the geometry of inorganic complexes were completely verified twenty years later, through the application of the technique of x-ray diffraction. 

Certain groups of organocobalt(III) complexes have been dealt with in previous reviews. The organo-corrinoids have been mentioned in all reviews on vitamin B, 2 since 1961, when the coenzyme form was identified as an organometallic compound [see, for example, (79, 178) and references therein]. The literature on the corrinoids is too extensive to be treated comprehensively here and for details and references readers are referred to the book on The Inorganic Chemistry of Vitamin B,2 (136)certain other aspects of the organometallic chemistry of cobalt corrinoids are treated elsewhere (137). The pentacyanides were reviewed in 1967 (105), the DMG complexes (cobaloximes) in 1968 (145), and some aspects of salen, BAE, and related complexes in 1970 (17). 

Mohamed, A.A., Kani, I., Ramirez, A.O. and Fackler, J.P. Jr (2004) Synthesis, characterization, and luminescent properties of dinuclear gold(I) xanthate complexes X-ray structure of [Au2(nBu-xanthate)2j. Inorganic Chemistry, 43, 3833-3839. 

Abdou, H.E., Mohamed, A.A. and Fackler, J.P. Jr (2007) Oxidative-addition to the dinuclear Au(I) amidinate complex, [Au2(2,6-(CH3)2Ph-form)2]. Syntheses and characterization of the Au(II) amidinate complexes. The first dinuclear Gold(Il) nitrogen complex possessing bonds to oxygen. Inorganic Chemistry, 46, 9692-9699. 

Mohamed, A.A., Abdou, H.E. and Fackler, J.P. Jr (2006) Mercury(ll) cyanide coordination polymer with dinuclear gold (1) amidinate. Structure of the 2-D [Au2(2,6-Me2-formamidinate)2]-2Hg (CN)2 2THF complex. Inorganic Chemistry, 45, 11-12. 

Barber J., Elduque, A., Gimenez, R., Lahoz, F.J., Oro, L.A. and Serrano, J.L. (1998) (Pyrazolato)gold complexes showing room-temperature columnar mesophases. Synthesis, properties, and structural characterization. Inorganic Chemistry, 37, 2960-2967. 

Oyaizu, K., Ohtani, Y, Shiozawa, A., Sugawara, K, Saito, T. and Yuasa, M. (2005) Highly stable gold(III) complex with a hydantoin ligand in alkaline media. Inorganic Chemistry, 44, 6915. 

Manassero, M. (2003) Synthesis and characterization of mononuclear amidogold(III) complexes - Crystal structure of [Au(N2C]oH7(CMe2C6H4)-6](NHC6H3Me2-2,6)][PF6] - Oxidation of 4-methylaniline to azotoluene. European Journal of Inorganic Chemistry, 2304. 

Zhu, S., Gorski, W., Powell, D.R. and Walmsley, J.A. (2006) Synthesis, structures, and electrochemistry of gold(III) ethylenediamine complexes and interactions with guanosme 5 -monophosphate. Inorganic Chemistry,... 

Mansour, M.A., Lachicotte, R.J., Gysling, H.J. and Eisenberg, R. (1998) Syntheses, molecular structures, and spectroscopy of gold(III) dithiolate complexes. Inorganic Chemistry, 37, 4625. 

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