Strontium amide

Prior to the previous edition of this book, no examples of substituted strontium amides had been well characterized. Even now, only a few strontium amide crystal structures are known and have been briefly reviewed in the context of more general aspects of the chemistry of group 2 metal compounds.  

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As exemplified by the complex [Sr N(SiMe3)2 2(dme)2], a coordination number of six rather than four is often observed in monomeric strontium amides because of the relatively... 

Magnesium reacts slowly at lower temperatures to give the amide, as do all active metals this reaction is catalyzed by transition metal ions. Aluminum nitride [24304-00-5] AIN, barium nitride [12047-79-9] Ba2N2, calcium nitride [12013-82-0] Ca2N2, strontium nitride [12033-82-8], Sr2N2, and titanium nitride [25583-20-4], TiN, may be formed by heating the corresponding amides. 

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],... 

Even a cursory reading of Chapter 3 of the previous volume/ dealing with alkaline earth diorgano amides, shows that detailed information on their preparation, structure and reactivity was quite sparse. For example, there were no data available for strontium or barium amide derivatives and there was just one structure of a complex related to a calcium amide - that of [(thf)3Ca( AIH j(. - in which calcium was incorporated as part of an... 

Amide. — It has been pointed out before that europium behaves more or less like the alkaline earths and is closely related to strontium and barium. It is found to react with liquid ammonia at —78° C in much the same way as the alkali metals forming a characteristic deep blue solution. Eu(NH2)2 can be isolated [260] from the blue solution. Recent electron paramagnetic studies [261] of solutions of europium in liquid ammonia showed the presence of complex hyperfine lines arising from Eu2+ (8 7/2, g — 1.990 0.002) besides the characteristic single line of the solvated electron (g = 2.0014 0.0002) K The departure of the Eu2+ <7-value from the free electron value is explained as being due to spin-orbit coupling and a slight admixture (3.5%) of the 6P7/2 state. 

Strontium Diazide A620-L Styrylamine. See Aminostyrene A257-L Succinum. See Amber A165-R Sulfurless Black Powder. See under Amide (Explosif) A168-L Sulfuryl Diazide A621-R Sylvie Acid. See Abietic Acid A2-R... 

Silicon, higher chlorides of, 42 Silicon tetrabromide, 38, 40 Silicon tetrachloride, 44 Silicopropane, octachloro, 44 Silicotungstic acid, 129 analysis, 131 ether complex, 131 Silver, metallic, 4 Silver chloride, reduction of, 3 Silver cyanamide, 98 Silver residues, purification of, 2 Sodium amalgam, 10 Sodium amide, 74 Sodium azide, purification of, 79 Sodium azidodithiocarbonate, 82 Sodium butoxide, 88 Sodium hypochlorite (solution), 90 Sodium iodate, 168 Sodium metaperiodate, 170 Sodium paraperiodate, chlorine method, 169 persulfate method, 170 Strontium amalgam, 11 Sulfur hexafluoride, 121 Sulfuryl chloride, 114... 

Several classes of synthesized calixarenes bearing several moieties (ether, ester, and amide derivatives), were tested for the extraction of strontium picrates (from aqueous solutions into dichloromethane).128 Only a few of them show appreciable extraction levels. The p-i-butyl calix[6]arene hexa(di-/V-ethyl)amide (CA4) shows a very high extraction level of alkaline earth cations with respect to alkali metal cations. Moreover, dealkylation of the calix[6]arene hcxa(di-/V-cthyl)amidc (CA5) decreases the extraction of both sodium and strontium. As this decrease is much more important for sodium than for strontium, the Sr/Na selectivity, which increases from 3.12 to 9.4, is better than that achieved for DC18 derivative under the same conditions (8.7). These results were confirmed by extraction of strontium (5 x 10 4 M) from 1 M HN03 solutions, where it was found that p-t-butyl calix[4]arene tetra(di-N-ethyl) amide (CA2) (10 2 M in NPOE) extracts only sodium (DNa = 12.3, DSl < 0.001). 

Increasing the size of calixarenes favors the extraction of strontium and leads to a decrease of sodium extraction. For p-t-butyl calix[5]arene pcnta(di-/V-pcntyl)amide (CA3) (10-2 M in NPOE), DNa = 0.79, DSl = 1.5. For p-t-butyl calix[6]arene hexa (di-A-ethyl)amide (CA4) (5 x 10 3 M in NPOE), DNa = 0.05, DSl=3.8. Under the same conditions (HN031 M), this compound displays higher selectivity than DC18C6. 

Quantum mechanis (QM) calculations showed that the interaction energy between strontium and amide carbonyl groups increased in the expected sequence primary < secondary < tertiary amides, but could not explain the difference of complexation between (CA1) and (CA2), in particular in chloroform.129 Another hypothesis based on the loss of internal H-bonds with the NH2 protons was also rejected. MD simulations of Sr(Pic)2 complexes of (CA1) and (CA2) for 1 ns at the water/chloroform... 

It was shown that narrow-rim CMPO derivatives form stronger 1 1 lanthanide complexes than their wide-rim counterparts. However, lanthanide extraction results display a stronger extracting ability. This discrepancy can be explained by the fact that, contrary to the wide-rim CMPO calixarenes that form polymeric species, a part of less lipophilic monomeric narrow-rim CMPO calixarene piles up at the interface instead of being extracted, as predicted by Wipff for the extraction of strontium by mixed amide calixarenes (see Section 4.4.1.1). This assumption is all the more... 

Ammonia dissolves alkali metals, barium, calcium and strontium and forms an unstable blue solution. This solution contains the metal ion and free electrons that slowly decompose, release hydrogen and form the metal amide. Compared to water, liquid ammonia is less likely to release protons (H+ ions), is more likely to take up protons (to form NH4+ ions) and is a stronger reducing agent219. 

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