Hydrides, binary bonding

Hydrides are compounds that contain hydrogen (qv) in a reduced or electron-rich state. Hydrides may be either simple binary compounds or complex ones. In the former, the negative hydrogen is bonded ionicaHy or covalendy to a metal, or is present as a soHd solution in the metal lattice. In the latter, which comprise a large group of chemical compounds, complex hydridic anions such as BH, A1H, and derivatives of these, exist. 

Because they possess an odd number of valence electrons the elements of this group can only satisfy the 18-electron rule in their carbonyls if M-M bonds are present. In accord with this, mononuclear carbonyls are not formed. Instead [M2(CO)s], [M4(CO)i2] and [M6(CO)i6] are the principal binary carbonyls of these elements. But reduction of [Co2(CO)g] with, for instance, sodium amalgam in benzene yields the monomeric and tetrahedral, 18-electron ion, [Co(CO)4] , acidification of which gives the pale yellow hydride, [HCo(CO)4]. Reductions employing Na metal in liquid NH3 yield the super-reduced [M(CO)3] (M = Co, Rh, Ir) containing these elements in their lowest formal oxidation state. 

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 ... 

Because of their low intrinsic electronegativities, neutral late transition metals (bearing an abundance of lone pairs) can serve as good donors in nM— ctah interactions of the form (5.69a). Furthermore, transition-metal-hydride bonds (Section 4.4.1) often display sufficient covalency or polar-covalency (particularly in transition-metal cations) to serve as good acceptors in ns— ctmh interactions of the form (5.69b). In the present section we shall briefly examine the simple example of platinum dihydride (PtH2) as a water-mimic in binary H-bonded complexes with H20,... 

You can see the effect of hydrogen bonding clearly in the boiling point data of the binary hydrides of Groups 14 to 17 (IVA to VIIA), shown in Figure 4.16. In Group 14, the trend in boiling point is as expected. 

This chapter commences with a review of a limited number of ternary hydride systems that have two common features. First, at least one of the two metal constituents is an alkali or alkaline earth element which independently forms a binary hydride with a metal hydrogen bond that is characterized as saline or ionic. The second metal, for the most part, is near the end of the d-electron series and with the exception of palladium, is not known to form binary hydrides that are stable at room temperature. This review stems from our own more specific interest in preparing and characterizing ternary hydrides where one of the metals is europium or ytterbium and the other is a rarer platinum metal. The similarity between the crystal chemistry of these di-valent rare earths and Ca2+ and Sr2+ is well known so that in our systems, europium and ytterbium in their di-valent oxidation states are viewed as pseudoalkaline earth elements. 

Apart from the binary hydrides of Groups 16 and 17, Lowry/ Brpnsted acids in aqueous solution are nearly all oxoacids, i.e. substances containing O-H bonds which ionise in aqueous solution to give oxo-anions and H+(aq) (or H30+). Most oxoacids are molecular hydroxides E(OH) , such as B(OH)3, Ge(OH)4 and Te(OH)6, or oxohydroxides EOm(OH) . In addition, we have more complex species containing E-E bonds or E-O-E bridges. In EOm(OH) - for example, N02(0H), PO(OH)3, S02(0H)2,103(0H) - the m O atoms are held to E by bonds having at least some double bond character, via p -p or d -p overlap. Oxohydroxides may be seen as being derived from hydroxides by elimination of H20, and are favoured by elements E whose atoms form double bonds to O atoms. 

These methods are, mutatis mutandis, applicable to the formation of E-H and E-X (X = halogen) bonds in compounds other than binary hydrides and halides. 

The direct formation of a binary hydride EH from the elemental substances is usually favoured thermodynamically if E is much lower, or much higher, in electronegativity than H. Thus, for example, the free energies of formation AG of LiH and HC1 are respectively —68 and -95 kJ mol-1. In the case of HC1, it can be predicted from the relevant bond energies - rationalised in terms of Pauling s derivation of electronegativities - that the formation of HCl(g) from the elemental substances should be exothermic. Further, entropy considerations will favour the randomisation of atoms in molecules. For the reaction ... 

The data on character of chemical bonds in binary hydrides of Ti, Zr, Hf [7] obtained by us by X-Ray absorption spectroscopy method testify about the existence of correlation between the degree of ionicity of Me-H bonds in hydrides... 

The EDA analysis is performed with the geometry optimized by the plane-wave pseudopotential method. For binary hydrides, MH , the respective atomic energy densities of M and H are related closely to the nature of the chemical bond... 

Needless to say, when the hydrides have a resemblance in the chemical bonding state, their locations are close to each other in the diagram. For example, any binary hydrides of transition elements appear in the higher AEh region than those of typical elements. This indicates that transition elements could... 

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