Periodates transition metal complexes

The racemization mechanism of sec-alcohols has been widely studied [16,17]. Metal complexes of the main groups of the periodic table react through a direct transfer of hydrogen (concerted process), such as aluminum complexes in Meerwein-Ponn-dorf-Verley-Oppenauer reaction. However, racemization catalyzed by transition metal complexes occurs via hydrogen transfer processes through metal hydrides or metal dihydrides intermediates (Figure 4.5) [18]. 

While r 2-coordination of silanimines has been realized in species such as Cp2Zr(r 2-SiMe2=Nt-Bu)(PMe3) [13], no -(silanimine) transition metal complexes are known so far [14 - 16]. Access to these Si=N systems is opened up by treatment of 19b,c with Me3P=CH2 at low temperature leading to elimination of hydrogen chloride and formation of the fert-butyl and mesityl-N-derivative 23a,b. These species are stable only for a short period in solution (two hours in toluene at -30°C), but can be... 

As to the first route, we started in 1969 (1) in investigating unconventional transition metal complexes of the 5 and 4f block elements of periodic table, e.g., actinides and lanthanides as catalysts for the polymerization of dienes (butadiene and isoprene) with an extremely high cis content. Even a small increase of cistacticity in the vicinity of 100% has an important effect on crystallization and consequently on elastomer processability and properties (2). The f-block elements have unique electronic and stereochemical characteristics and give the possibility of a participation of the f-electrons in the metal ligand bond. 

Metal complexes of stable carbenes are now known for almost all the metals of the periodic table. This chapter is divided into an overview of the NHC-main-group metal adducts that are generally synthesized by adding the free NHC to an appropriate metal precursor and a discussion of the various synthetic approaches toward transition metal complexes. 

NMR (CeDg, 125.7 MHz, 25°C) 139.8, 132.5, 128.8-129.1 (overlapping resonances), 124.6, 17.0 (br). B NMR (CgDg, 128.3 MHz, 25°C) -10.96 ppm. The compound is a versatile precursor to a wide range of transition metal complexes supported by the tris(phosphino)borate ligand. It is air- and water-stable for extended periods, and, unlike the lithium and ammonium salts of [PhB(CH2PPh2)3] , it is both soluble and stable in chloroform and dichloromethane for days, making these useful solvents available for subsequent trans-metallation chemistry. 

Although studies of chemical reactions on transition-metal surfaces take place under very different conditions than chemical reactions catalyzed by discrete transition-metal complexes, several similarities are apparent, as indicated here. We are now in a periode of time where both experimental techniques and theoretical calculations are beginning to provide us with a picture of how chemical reactions on transition-metal surfaces take place - hopefully these studies will provoke others to try to develop discrete systems with similar properties, and thus show us that reac-... 

Transition metal complexes containing fluorinated ligands date back to the initial explosive development of organometallic chemistry in the period from 1950 to 1970, and some early reviews contain a great deal of useful and relevant information (3,6,7). Early work clearly established that these compounds do indeed exhibit dramatically different structural, bonding, and chemical... 

The program and force field SHAPES, developed for transition metal complexes and tested for square planar geometries, uses a single Fourier term (Eq. 2.19), which is similar to the torsional angle term in many molecular mechanics programs (see Section 2.2.3 periodicity = m, phase shift = Fourier force constant kg is related to that of the harmonic potential, kg (Eq. 2.7) by Eq. 2.20. 

Until recently, the development and applications of TDDFT were directed, chiefly, at atoms and prototype molecules of elements from main groups of the periodic table. Application of TDDFT to transition metal complexes remains a challenge, and this review article presents recent examples of such applications. All chemical applications share the same basic theory and approximations, the main features of which will be outlined below. 

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