Alkaline earth metal amides calcium

Carbene complexes of alkaline earth metal amides and metallocenes have also been reported. Reaction of calcium, strontium, and barium bis(trimethylsilyl)amides [M(N(SiMe3)2 2(thf)2] (M = Ca, Sr, Ba) with two equivalents... 

The coordination catalysts for these reactions are diverse. They can be compounds of alkaline earth metals, like calcium amide, or calcium amide-alkoxide. They can also be Ziegler-Natta-type catalysts. These can be alkoxides of aluminum, magnesium, or zinc combined with ferric chloride. Others are reaction products of dialkylzinc with water or alcohol. They can also be bimetallic //-oxoalkoxides, such as [(RO)2A102]Zn. Other catalysts are aluminum or zinc metalloporphyrin derivatives (see Fig. 4.1). 

The heavier alkaline earth metals Ca, Sr, Ba (and Ra) react even more readily with non-metals, and again the direct formation of nitrides M3N2 is notable. Other products are similar though the hydrides are more stable (p. 65) and the carbides less stable than for Be and Mg. There is also a tendency, previously noted for the alkali metals (p. 84), to form peroxides MO2 of increasing stability in addition to the normal oxides MO. Calcium, Sr and Ba dissolve in liquid NH3 to give deep blue-black solutions from which lustrous, coppery, ammoniates M(NH3)g can be recovered on evaporation these ammoniates gradually decompose to the corresponding amides, especially in the presence of catalysts ... 

It is also possible to isolate bis(carbene) complexes involving the heavier alkaline earth metals. Thus, the reaction of two equivalents of 4 (R = Me or (Bu, R = H) with calcium, strontium and barium bis(trimethylsilyl)amides [M N(SiMe3)2 2(thf)2] (M = Ca, Sr, Ba) resulted in the displacement of two thf molecules to afford the corresponding biscarbene species, 19 (19). The solubilities and stabilities of these complexes were found to decrease from calcium to barium. 

The metalation of trialkylsilylphosphane and -arsane with the alkaline earth metal bis[bis(trimethylsilyl)amides] of calcium, strontium, and barium yields the mixed phosphanides and phosphanediides as well as arsanides and arsanediides depending on the stoichiometry and the demand of the trialkylsily] substituents according to Scheme 3.6-11. The main feature is the M2E3 bipyramid with the metal atoms in apical positions. These cages are often interconnected via common faces (61, 63, 64, 65, 67, and 69). A substitution of the phosphanide substituents by other Lewis bases such as THF or benzonitrile is not possible for these compounds and, consequently, homoleptic phosphanediides and arsanediides with inner M4E4 heterocubane moieties are so far unknown for M = Ca, Sr, and Ba. In all these cases a further metalation to obtain homoleptic phosphanediides failed. 

The synthesis of heterobimetallic cages which contain alkaline-earth metals and tin(+2) atoms succeeds by the metalation of trialkylsilyl substituted phosphanes with the bis(trimethylsilyl)amides of tin(+2) and of calcium, strontium, or barium according to Scheme 3.6-13. Heterobimetallic cages of tin and magnesium are unknown, instead their formation mixtures of the homometallic phosphanides are observed [75],... 

The formation of alkaline earth metal bis[bis(tiialkylsilyl)amides] has been discussed in detail elsewhere." Like all heavier group 2 metal bis[bis(tiisalkylsilyl)amides], the complex [(Ca N(SiMe3)2 2)2] has a dimeric structure both in solution and the solid state (Figure 3.8), in which the calcium atoms are in a distorted trigonal planar environment. 

Led by the efforts of Westerhausen and coworkers, a variety of heavy alkaline earth metal zincates or aluminates under formation of alkaline earth metal-carbon contacts have been prepared. Examples include the reaction of trialkylalanes with donor-free calcium i)fr-amides to afford dimeric aluminates, shown in Figure 30. Noteworthy is the planar Ca2N2 center of this complex, in addition to close calcium-aluminum contacts, which may indicate the presence of three-center, two-electron bonding. 

Syntheses that exploit the solubility of the alkaline-earth metals in liquid ammonia have proven practical for alkoxide work, as they generate high yields, reaction rates, and purity (Table 8, Equation (3)). In a refinement of this approach, Caulton and co-workers have used dissolved ammonia in an ethereal solvent, usually THF, to effect the production of a number of alkoxides of barium, and this method has also been examined with calcium and strontium (Table 8, Equations (4a) to (4c)). Displacement reactions using alkali metal alkoxides and alkaline-earth dihalides (Table 8, Equation (5)), and between alkaline-earth hydrides or amides and alcohols (Table 8, Equations (6) and (7)), have been examined, but alkali-metal halide impurities, incomplete reactions, and unexpected equilibria and byproducts can affect the usefulness of these approaches. 

A comparison of these compounds with the corresponding zinc derivatives should clarify the influence of the empty d orbitals involved in the bonding situation of the alkaline earth metal bis(phosphanides). Whereas zinc bis[bis(trimethylsilyl)amide] is monomeric due to the steric demand of the bulky amide ligand [6], the trimethylsilyl substituted phosphanide leads to oligomers such as dimers or trimers [7], The influence of the pnicogen atom is small, thus the phosphorus and arsenic derivatives (Fig. 5.) look very similar [8] or even crystallize isotypically. In contrast to the d metals calcium, strontium and barium, zinc derivatives solely build up monocyclic ring systems. 

As in the 1960s the demand for (3-pinene far exceeded its availability owing to its versatile applications, a large part of the more commonly occurring a-pinene was isomerized to (3-pinene using, for example, basic catalysts such as calcium amide and alkaline earth metal oxides. A major amount of (3-pincnc is converted to resins with adhesive properties and by pyrolysis to the acyclic monoterpene myrcene. 

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