Objections to a Proof of Molecular Asymmetry of Optically Active Phenylaminoacetic Acid

Abstract

The evidence thus obtained leads us to conclude that element 87 occurs in samarskite. Furthermore, this element yields a chloride volatilizable at 1000°, and its alum is the least soluble in the alkali series. A name for the element will not be announced until additional confirmatory data are obtained.

Odd‐Electron Bonds

“…The series with ammonia as the closed-shell partner deviates strongly from those with NCl 3 and NMe 3 .F or NCl 3 ,t he data-points all lie together,s ot hat no correlation is discernible. The coefficients of determination( R 2 )a re very high for NH 3 and NMe 3 (0.99 and 1.00, respectively)b ut in each case only for three points (F,C l and Br). More significantly, the correlation lines do not pass through the origin with constantsi nt he regression equations of + 3.9 and À12.6 kcal mol À1 ,respectively.…”

“…Above all, much of the late Dieter Asmus' seminalw ork [4][5][6][7][8][9][10][11][12][13] has apparently been forgotten, [72] but also the pioneering experimental studies of Meot-Ner, [19] Pauling [3] and Hiberty's [29] rationalization of oddelectron bond energiesi nt erms of valence-bond theory and Bock [34] and Nelsen's [35] fundamental studies on three-electron p-bonds are apparently no longerp resenti no ur general picture of bondingt heory.T his short review attempts to remind us of these classical examples of physicalo rganic chemistry, which taken on an even more importantr ole as the importance of radicals and radical ions is increasingly recognized in both biology and photovoltaics and whose importance in transition-metal chemistry has recently been reviewed. [73] Computational Section All calculations used the Gaussian 09 series of programs.…”

“…However,t his picture is at odds with Pauling's perceptive analysiso fo ne and three-electron bonds, [3] published in 1931, and Baird [4] pointed out quite early that the simplei dea of "half bonds" is not correct,e ven within as emi-quantitative picture. Theoretical interest in odd-electron bonding was strengthened by Asmus' observation of intramolecular SÀS three-electron bonds in solution.…”

“…He found the complexation energies to be strongestf or partnersw ithe qual ionization potentials and to fall off very steeply with increasingd ifference between the ionization potentials of then eutral molecules of the complexed species, as had been predicted by Pauling in 1931. [3] The theory of odd-electron s-bonds was established over at least ad ecade. The simplest one-electron bondeds pecies, H 2 + C,w as well known experimentally and had been the subject of numeroust heoretical studies because it only has one electron.…”

Hartree−Fock−Heitler−London Method. 2. First and Second Row Diatomic Hydrides

“…However, we recall that at Z ) 13 the atomic correlation energy and the relativistic correction are nearly equal in value. We used the following basis sets: for the H atom [10,5,4,/ 6,5,4] in the hydrides and [10,5,4,4] in the H 2 and HeH molecules; for the He atom [14,9,8,5,2]; for the Li atom [15,-10,6,1/10,8,6,1]; for the Be atom [17,8,6,3/11,8,6,3]; for the B atom [15,11,7,5/9,8,6,4]; for the C atom [17,13,6,5/11,8,5,4]; for the N and O atoms [17,13,5,4/9,7,5,4], and for the F atom [18,13,5,4/12,6,5,4]. These basis sets yield the Hartree-Fock atomic ground-state energies given in Table 1.…”