Metal/element hydrides

Most literature reports have utilized some type of pre-injection deriva-tization for TBT and the other butyltin species. Such approaches have generally used hydridization or alkylation, in order to provide improved GC performance characteristics for the original species. Improvements in the off-column derivatization methods generally reported have quite recently used reaction GC to form the hydrides of TBT and its analogs prior to FPD detection [62-64]. This remains an entirely feasible, continuous, and automatable approach to perform on-column reactions in GC, especially for compounds such as TBT which can readily form metal/element hydrides. 

Hydrogen reacts direcdy with a number of metallic elements to form hydrides (qv). The ionic or saline hydrides ate formed from the reaction of hydrogen with the alkali metals and with some of the alkaline-eartb metals. The saline hydrides ate salt-like in character and contain the hydride, ie,, ion. Saline hydrides form when pure metals and H2 react at elevated temperatures (300—700°C). Examples of these reactions ate... 

Fig. 3.11. Numerous examples are also known in which hydrogen acts as a bridge between metallic elements in binary and more complex hydrides, and some of these will be mentioned in the following section which considers the general question of the hydrides of the elements.

K. M. Mackay, Hydrogen Compounds of the Metallic Elements, E. and F. N. Spon, London, 1966, 168 pp. Hydrides, Comprehensive Inorganic Chemistry, Vol. 1, Chap. 2, Pergamon Press, Oxford, 1973. 

Attempts to classify carbides according to structure or bond type meet the same difficulties as were encountered with hydrides (p. 64) and borides (p. 145) and for the same reasons. The general trends in properties of the three groups of compounds are, however, broadly similar, being most polar (ionic) for the electropositive metals, most covalent (molecular) for the electronegative non-metals and somewhat complex (interstitial) for the elements in the centre of the d block. There are also several elements with poorly characterized, unstable, or non-existent carbides, namely the later transition elements (Groups 11 and 12), the platinum metals, and the post transition-metal elements in Group 13. 

Such reactions are discussed at appropriate points throughout the book as each individual compound is being considered. A particularly important set of reactions in this category is the synthesis of element hydrides by hydrolysis of certain sulfides (to give H2S), nitrides (to give NH3), phosphides (PH3), carbides (C Hm), borides (B Hm), etc. Useful reviews are available on hydrometallurgy (the recovery of metals by use of aqueous solutions at relatively low temperatures), hydrothermal syntheses and the use of supercritical water as a reaction medium for chemistry. 

The nature of a binary hydride is related to the characteristics of the element bonded to hydrogen (Fig. 14.8). Strongly electropositive metallic elements form ionic compounds with hydrogen in which the latter is present as a hydride ion, H. These ionic compounds are called saline hydrides (or saltlike hydrides). They are formed by all members of the s block, with the exception of beryllium, and are made by heating the metal in hydrogen ... 

An obvious limitation to the hydrogen-elimination method, especially for early transition metal elements, is the availability of transition metal hydrides (this applies also to the HCl elimination) or binuclear complexes. 

Metal hydrides containing transition metal (TM)-hydrogen complexes, with the transition metal in a formally low oxidation state, are of fundamental interest for clarifying how an electron-rich metal atom can be stabilized without access to the conventional mechanism for relieving the electron density by back-donation to suitable ligand orbitals. By reacting electropositive alkali or alkaline earth metals ( -elements) with group 7, 8, 9, and 10 transition metals in... 

MCS-type reactions can occur while milling a simple metal hydride with a metallic element M,... 

Kamegawa et al. [156] synthesized MgjLaH, MgjCeHj, and MgjPrH, from powders of elemental metals. These hydrides decomposed into Mg and RE-hydride at about 300°C with an endothermic reaction. Obviously, because of the high pressures involved in their synthesis, the hydrides are irreversible. 

Figure 5.20 Table of the binary hydrides and the Allred-Rochow electronegativity [26], Most elements react with hydrogen to form ionic, covalent or metallic binary hydrides.

Toxicity Variable. The hydrides of phosphorus, arsenic, sulfur, selenium, tellurium and boron which are highly toxic, produce local irritation and destroy red blood cells. They are particularly dangerous because of their volatility and ease of entry into the body. The hydrides of the alkali metals, alkaline earths, aluminum, zirconium and titanium react with moisture to evolve hydrogen and leave behind the hydroxide of the metallic element. This hydroxide is usually caustic. See also sodium hydroxide... 

When discussing metal alloys (Section 4.3), we saw that atoms of non-metallic elements such as H, B, C, and N can be inserted into the interstices (tetrahedral and octahedral holes) of a lattice of metal atoms to form metal-like compounds that are usually nonstoichiometric and have considerable technological importance. These interstitial compounds are commonly referred to as metal hydrides, borides, carbides, or nitrides, but the implication that they contain the anions H, B3, C4, or N3- is misleading. To clarify this point, we consider first the properties of truly ionic hydrides, carbides, and nitrides. 

In the early 1960s it was recognized (6,187) that there were bonding similarities between the pentagonal face of the isomeric [nirio-(y HjJ2- ions and the well-known cyclopentadienide ion (Cp ) [CydJ- (Fig. 16). The isomeric nido-C2B9H1 J2- ions, which are commonly known as dicarbollide ions, and many other carborane anions, form stable complexes with most of the metallic elements. Indeed nearly all metals can be combined with polyborane hydride clusters to produce an apparently limitless variety of cluster compounds. 

Hydrogen is unusual because it can form both a cation (H+) and an anion (H ). Moreover, its intermediate electronegativity means that it can also form covalent bonds with all elements except metals. The hydrides were introduced in Section 14.3. Because hydrogen forms compounds with so many elements (Table 14.2), we shall meet more of its compounds when we study the other elements. 

Of the monomeric metal carbonyl hydrides [HMn(CO)s,H2Fe(CO)4,HCo(CO)4], only HMn(CO)s has been analyzed crystallographically 10 4S). The lack of results for H2Fe(CO)4 and HCo(CO)4 is probably related to the fact that the compounds are thermally unstable. The neutron diffraction analysis of HMn(CO)s by La Placa and co-workers45) produced a Mn—H distance of 1.60(2) A. This result, together with the earlier measurement of the Re—H distance of 1.68(1)A in K2ReH9, provided conclusive proof that M—H distances in metal hydride complexes are normal (i.e., are consistent with the known covalent radii of the elements), and not anomalously short as suggested by some researchers (this controversy is reviewed in Refs. 1—3). 

Not all metallic elements form hydrides. Those that do, can be classified as follows ... 

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