Transition metals Several series

Transition metals several series of elements in which inner orbitals (d or / orbitals) are being filled. (12.13 18.1) Transuranium elements the elements beyond uranium that are made artificially by particle bombardment. (21.3)... 

Transition metals several series of elements in which inner orbitals (d or f orbitals) are being filled. 

Our discussion of the Irving-Williams series illustrates, as ever, an important generalization in transition-metal chemistry in many cases there is no single, simple principle which may be invoked to rationalize a given series of observations. Whilst LFSE effects are very important, they are but one of several factors controlling structure and thermodynamics. 

Several patents dealing with the use of volatile metal amidinate complexes in MOCVD or ALD processes have appeared in the literature.The use of volatile amidinato complexes of Al, Ga, and In in the chemical vapor deposition of the respective nitrides has been reported. For example, [PhC(NPh)2]2GaMe was prepared in 68% yield from GaMes and N,N -diphenylbenzamidine in toluene. Various samples of this and related complexes could be heated to 600 °C in N2 to give GaN. A series of homoleptic metal amidinates of the general type [MIRCfNROilnl (R = Me, Bu R = Pr, BuO has been prepared for the transition metals Ti, V, Mn, Fe, Co, Ni, Cu, Ag, and La. The types of products are summarized in Scheme 226. The new compounds were found to have properties well-suited for use as precursors for atomic layer deposition (ALD) of thin films. 

In the previous volume of this series, an article entitled Organo-Transition Metal Chemistry—A Guide to the Literature 1950-1970 (1) attempted to list a majority of the textual sources of information concerning transition metal organometallics which have appeared over the last two decades. Since the preparation of that survey, a large number of important new contributions have appeared. In the present account, the new review literature has been surveyed up to the end of 1971. In addition, several books and articles omitted from the earlier survey are included. 

The rules above gave maximum and minimum oxidation numbers, but those might not be the only oxidation numbers or even the most important oxidation numbers for an element. Elements of the last six groups of the periodic table for example may have several oxidation numbers in their compounds, most of which vary from each other in steps of 2. For example, the major oxidation states of chlorine in its compounds are -1, +1, +3, +5, and +7. The transition metals have oxidation numbers that may vary from each other in steps of 1. The inner transition elements mostly form oxidation states of + 3, but the first part of the actinoid series acts more like transition elements and the elements have... 

Abstract Amino acids are the basic building blocks in the chemistry of life. This chapter describes the controllable assembly, structures and properties of lathanide(III)-transition metal-amino acid clusters developed recently by our group. The effects on the assembly of several factors of influence, such as presence of a secondary ligand, lanthanides, crystallization conditions, the ratio of metal ions to amino acids, and transition metal ions have been expounded. The dynamic balance of metalloligands and the substitution of weak coordination bonds account for the occurrence of diverse structures in this series of compounds. 

Amino acid is one of the most important biological ligands. Researches on the coordination of metal-amino acid complexes will help us better understand the complicated behavior of the active site in a metal enzyme. Up to now many Ln-amino acid complexes [50] and 1 1 or 1 2 transition metal-amino acid complexes [51] with the structural motifs of mononuclear entity or chain have been synthesized. Recently, a series of polynuclear lanthanide clusters with amino acid as a ligand were reported (most of them display a Ln404-cubane structural motif) [52]. It is also well known that amino acids are useful ligands for the construction of polynuclear copper clusters [53-56], Several studies on polynuclear transition metal clusters with amino acids as ligands, such as [C03] [57,58], [Co2Pt2] [59], [Zn6] [60], and [Fe ] [61] were also reported. 

In the framework of CUORICINO [41] and CUORE [42] experiments (see Section 16.5), Ge crystal wafers of natural isotopic composition have been doped by neutron irradiation, and the heavy doping led to materials close to the metal insulator transition. Several series of NTD wafers with different doping have been produced [43], After an implantation and metallization process on both sides of the wafers, thermistors of different sizes can be obtained by cutting the wafers and providing electrical contacts. 

Eq. (8) requires determination of the two-electron oxidation potential of L M by electrochemical methods. When combined with the two-electron reduction of protons in Eq. (9), the sum provides Eq. (10), the AGh- values of which can be compared for a series of metal hydrides. Another way to determine the AGh-entails the thermochemical cycle is shown in Scheme 7.3. This method requires measurement of the K of Eq. (11) for a metal complex capable of heterolytic cleavage of H2, using a base (B), where the pK., of BH+ must be known in the solvent in which the other measurements are conducted. In several cases, Du-Bois et al. were able to demonstrate that the two methods gave the same results. The thermodynamic hydricity data (AGh- in CH3CN) for a series of metal hydrides are listed in Table 7.4. Transition metal hydrides exhibit a remarkably large range of thermodynamic hydricity, spanning some 30 kcal mol-1. 

Ffirai and Toshima have published several reports on the synthesis of transition-metal nanoparticles by alcoholic reduction of metal salts in the presence of a polymer such as polyvinylalcohol (PVA) or polyvinylpyrrolidone (PVP). This simple and reproducible process can be applied for the preparation of monometallic [32, 33] or bimetallic [34—39] nanoparticles. In this series of articles, the nanoparticles are characterized by different techniques such as transmission electronic microscopy (TEM), UV-visible spectroscopy, electron diffraction (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) or extended X-ray absorption fine structure (EXAFS, bimetallic systems). The great majority of the particles have a uniform size between 1 and 3 nm. These nanomaterials are efficient catalysts for olefin or diene hydrogenation under mild conditions (30°C, Ph2 = 1 bar)- In the case of bimetallic catalysts, the catalytic activity was seen to depend on their metal composition, and this may also have an influence on the selectivity of the partial hydrogenation of dienes. 

In the review by Kanatzidis et al. (2005), the preparation by the tin-flux method is mentioned also for several ternary phosphides and polyphosphides of rare-earth and transition metals. Typically the components (R metal, T metal, P and Sn in an atomic ratio of about 1 4 20 50) in sealed silica tubes were slowly heated, to avoid violent reactions, up to 800°C, annealed at that temperature for 1 week and slowly (2 K/h) cooled to ambient temperature. The tin-rich matrix was dissolved in diluted hydrochloric acid. The authors described the preparation of compounds corresponding for instance to the formula MeT4P12 (Me = heavy rare-earth metals and Th and U, T = Fe, Ru, etc.) and to the series of phases MeT2P2 (Me is a lanthanide or an actinide and T a late transition metal) having a structure related to the BaAl4 or ThCr2Si2 types. 

Crystallographic shear plane. Series of discrete shear phases are observed among the oxides of several transition metals. By progressive reduction, series of Ti 02 i, V 02 i phases are obtained from the dioxides, as Me 03 i phases may be related to trioxides such as M0O3 or WO3. An example of a crystallographic shear plane formation is schematically shown in Fig. 7.54. 

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