Isoelectronicity

Phosphorus pentafluoride PF will readily accept an electron pair from a fluoride ion F to form the stable hexafluorophosphate(V) anion PF C. This ion is isoelectronic with SF. and neither SF nor PF show any notable tendency to accept further electron pairs, though there is some evidence for the existence of an SF ion. 

In this case the covalency of boron is brought up to four because the donor molecule supplies the necessary electrons. The adduct formed, trimethylamine-borane, is a stable white solid. Other compounds of a similar kind are known, all derived from the simple structure H3N -> BH3. This compound is isoelectronic with ethane, i.e. it contains the same number of electrons and has the same shape. 

There are similar analogues to other aliphatic hydrocarbons, for example HjN BHj, which is isoelectronic with ethene, and a most interesting compound called borazine, B3N3H6, which possesses physical properties remarkably like those of the aromatic analogue ... 

Boron nitride is chemically unreactive, and can be melted at 3000 K by heating under pressure. It is a covalent compound, but the lack of volatility is due to the formation of giant molecules as in graphite or diamond (p. 163). The bond B—N is isoelectronic with C—C. 

Figure 2-125. Different isovalue-based surfaces of phenylalanine a) isoelectronic density b) molecular orbitals (HOMO-LUMO) c) isopotential surface and d) isosurface of the electron cryo-microscopic volume of the ribosome of Escherichia coii.

Hydrazories isoelectronic with ketones Comprehensive Organic Synthesis 1991, 2, 503... 

This was also an early example of the realization that for nearly all carbocations there exists a neutral isoelectronic isostructural boron an-alogne, which later proved itself so useful in the hands of my colleagnes R. E. Williams, G. K. S. Prakash, and L. Field. 

Whereas the proton (H ) can be considered the ultimate Bronsted acid (having no electron), the helium dication (He ) is an even stronger, doubly electron-deficient eleetron aceeptor. In a theoretical, calculational study we found that the helionitronium trication (NOaHe" ) has a minimum structure isoelectronic and isostructural... 

Isocyanide is isoelectronic with CO and a reactive compound in the presence of Pd catalysts. The heterobicyclic compound 127 is obtained by the successive insertion of 2.6-xylyl isocyanide (126) into the Pd-hydride bond formed from the hydrosilane[121. Aryl isocyanide inserts into the Si—Si bond in oligo-silanes. For example, 3 mol of 2,6-xylyl isocyanide insert into the tetrasilane 128 to give 129[122],... 

Indole is classified as a 7c-excessive aromatic compound. It is isoelectronic with naphthalene, with the heterocyclic nitrogen atom donating twm of the ten 7t-electrons. 

The fluoride ion is the least polarizable anion. It is small, having a diameter of 0.136 nm, 0.045 nm smaller than the chloride ion. The isoelectronic E and ions are the only anions of comparable size to many cations. These anions are about the same size as K" and Ba " and smaller than Rb" and Cs". The small size of E allows for high coordination numbers and leads to different crystal forms and solubiUties, and higher bond energies than are evidenced by the other haUdes. Bonds between fluorine and other elements are strong whereas the fluorine—fluorine bond is much weaker, 158.8 kj/mol (37.95 kcal/mol), than the chlorine—chlorine bond which is 242.58 kJ/mol (57.98 kcal/mol). This bond weakness relative to the second-row elements is also seen ia 0-0 and N—N single bonds and results from electronic repulsion. 

The hexafluorophosphates are among the most stable halogen complexes known. The highly symmetrical PF ion is stable to boiling aqueous alkaH and is decomposed only slowly in acidic solutions at ambient temperatures. It does hydrolyze rapidly at elevated temperatures in acid (85). The stabiHty of the PF 3 ion can be compared to the isoelectronic SF. The hexafluorophosphates can be decomposed yielding PF although in many cases only at temperatures where the PF reacts with the metal containers. Benzenediazonium hexafluorophosphate can be decomposed to PF, N2, and fluorobenzene at 120°C (86) and is a convenient source for laboratory amounts of PF as well as a frequently used catalyst. 

Fig. 1. Schematic diagram of semiconductor materials showing band gaps where CB and VB represent the conduction band and valence band, respectively and 0 and 0, mobile charge. The height of the curve represents the probabiUty of finding an electron with a given momentum bound to an N-isoelectronic impurity, (a) Direct band gap the conduction band minimum, F, is located where the electrons have 2ero momentum, ie, k = 0. The couples B—B, D—A, B—D, and B—A represent the various routes for radiative recombination. See text, (b) Indirect band gap the conduction band minimum, X, is located...

GaAs Pi V [x rX 0.35) homo GaAsP GaP (TS) no VPE diffused junction N-isoelectronic trap... 

Pyrrole has a planar, pentagonal (C2 ) stmcture and is aromatic in that it has a sextet of electrons. It is isoelectronic with the cyclopentadienyl anion. The TT-electrons are delocalized throughout the ring system, thus pyrrole is best characterized as a resonance hybrid, with contributing stmctures (1 5). These stmctures explain its lack of basicity (which is less than that of pyridine), its unexpectedly high acidity, and its pronounced aromatic character. The resonance energy which has been estimated at about 100 kj/mol (23.9 kcal/mol) is intermediate between that of furan and thiophene, or about two-thirds that of benzene (5). 

Boron forms B—N compounds that are isoelectronic with graphite (see Boron compounds, refractoryboron compounds). The small size also has a significant role in the interstitial alloy-type metal borides boron forms. Boron forms borides with metals that are less electronegative than itself including titanium, zirconium, and hafnium. 

B2qH240H] anion (75). Both B2QH24OH2 and [B2qH240H] are isoelectronic with the [B qH ] anion (77). The hydropolyborate ions formed by proton abstraction from decaborane are usehil intermediates for the preparation of metaHaboranes and heteroboranes. 

It is isoelectronic and isostmctural with the aluminum sandwich ion [i (9y y (9-3,3 -Al(3,l,2-AlC2B2H22)2]A shown iu Figure 26a. TThe siUcon is Tj -bonded iu unshpped fashion to the C2B2 faces of two dicarboUide cages. TThis bis-dicarboUide sUicon sandwich also forms adducts of a variety of stmctural types with Lewis bases such as pyridine and trimethylphosphine. 

A general type of stabilization for iminoboranes is a cyclodimerization, which yields diazadiboretidines (RBNR )2 that are isoelectronic with cyclobutadienes. 

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