Transitions trivalent chemistry

Fluorescent lifetimes of trivalent rare earth transition metal chemistry. G. E. Peterson, Transition Met. Chem. (N.Y.), 1966, 3, 202-302 (173). 

The properties of the lanthanide elements and their organometallic complexes described in the previous section explain in part why organo-met lic chemists in the past found lanthanide chemistry much less interesting than transition metal chemistry. The highly ionic, trivalent organolanthanide complexes appeared to have little potential to interact with the small-molecule substrates that provide such a rich chemistry for the transition metals neutral unsaturated hydrocarbons, H2, CO, phosphines, etc. The two-electron oxidation reduction cycles so important in catalytic transition metal chemistry in 18 16 electron complexes seemed... 

The cadmium(II) complex corresponding to 9 (M = Cd n = 2) was the first texaphyrin made [6], This aromatic expanded porphyrin was found to differ substantially from various porphyrin complexes and it was noted that its spectral and photophysical properties were such that it might prove useful as a PDT agent. However, it was also appreciated that the poor aqueous solubility and inherent toxicity of this particular metal complex would likely preclude its use in vivo [29-31], Nonetheless, the coordination chemistry of texaphyrins such as 9 was soon generalized to allow for the coordination of late first row transition metal (Mn(II), Co(II), Ni(II), Zn (II), Fe(III)) and trivalent lanthanide cations [26], This, in turn, opened up several possibilities for rational drag development. For instance, the Mn(II) texaphyrin complex was found to act as a peroxynitrite decomposition catalyst [32] and is being studied currently for possible use in treating amyotrophic lateral sclerosis. This work, which is outside the scope of this review, has recently been summarized by Crow [33],... 

Crystal chemistry of spinels. A classic example showing that transition metal ions display distinct site preferences in oxides stems from studies of spinel crystal chemistry. The spinel structure contains tetrahedral and octahedral sites normal and inverse forms exist in which divalent and trivalent ions, respectively, fill the tetrahedral sites. The type of spinel formed by a cation is related to its octahedral site preference energy (OSPE), or difference between crystal field stabilization energies in octahedral and tetrahedral coordinations in an oxide structure. Trivalent and divalent cations with large site preference energies (e.g., Cr3 and Ni2+) tend to form normal and inverse spinels, respectively. The type of spinel adopted by cations with zero CFSE (e.g., Fe3+ and Mn2+) is controlled by the preferences of the second cation in the structure. 

Investigations of the solid-state chemistry of the americium oxides have shown that americium has properties typical of the preceding elements uranium, neptunium, and plutonium as well as properties to be expected of a typical actinide element (preferred stability of the valence state 3-j-). As the production of ternary oxides of trivalent plutonium entails considerable difficulties, it may be justified to speak of a discontinuity in the solid-state chemical behavior in the transition from plutonium to americium. A similar discontinuous change in the solid-state chemical behavior is certainly expected in the transition Am Cm. Americium must be attributed an intermediate position among the neighboring elements which is much more pronounced in the reactions of the oxides than in those of the halides or the behavior in aqueous solution. 

Among the heavy post-transition metals there is a definite reluctance to exhibit the highest possible oxidation state. For example, boron is always trivalent, but thallium shows significant chemistry of the +1 oxidation state, leaving a pair of electrons coordinatively inert. This is known as the inert pair effect... 

The characteristic difference between the chemistry of elements outside the transition groups at one hand, and the d and f groups on the other hand, is that K (when it is defined) nearly always is an even integer in the former case, whereas the most stable (or most frequent) oxidation state of a transition element readily can have an odd K-value, such as Cr(III), Mn(II), Fe(III) or all the trivalent lanthanides from Ce(III) to Yb(III) with even Z. 

The first study of the solution chemistry of Rf was performed at Berkeley in 1970 and showed that Rf had a stable tetravalent state with properties similar to the gronp-4 elements Zr and Hf and different from Lr and the other trivalent actinides. This established that Rf shonld be placed in the Periodic Table as the heaviest member of group 4 and the first member of a new 6d transition series. It also confirmed the 1945 prediction of Seaborg that the actinide series should end with element 103. The first studies of the solution chemistry of element 105, condncted at the 88-Inch Cyclotron at Berkeley, were reported in 1988 and showed that the element behaved similarly to the group-5 elements Nb and Ta in its sorption properties, bnt differently from the group-4 elements. However, in extractions into certain organic solvents, Db(Ha) and Ta extracted but Nb did not, creating a renaissance of interest in more detailed studies of the behavior of element 105. 

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