"Try and fall sick .."-the composer, chemist, and surgeon Aleksandr Borodin.
Although Aleksandr Porfir’evič Borodin is considered one of the outstanding Russian composers of the 19th century, he left only a very small volume of musical work. He is particularly renowned for the world-famous “Polovtsian Dances” from the opera “Prince Igor” and for his membership in “The Mighty Handful”. Also noteworthy, aside from the forementioned opera “Prince Igor”, are his three symphonies, two string quartets, and a symphonic poem “In the Steppes of Central Asia”. The reason for his small œuvre is that he considered himself a sunday composer, composing for fun and only in his rare spare time or when he was ill. In fact, he was a professor of chemistry, and chemistry was avowedly his first passion. There were also other fields, besides chemistry, to which he was more committed than composition. Despite this declared priority for chemistry, Aleksandr Borodin is mostly unknown as a chemist to chemists of today, and—much to my regret—even as composer. This surely is not justified, since he is the discoverer of outstanding reactions, although unfortunately at a time when it was uncommon to name reactions after their inventors. This Essay is intended to shed light on all the various facets of Borodin, with a special focus on his chemical work.
Comprehensive thermochemistry of W-H bonding in the metal hydrides CpW(CO)2(IMes)H, [CpW(CO)2(IMes)H](•+), and [CpW(CO)2(IMes)(H)2]+. Influence of an N-heterocyclic carbene ligand on metal hydride bond energies.
The free energies interconnecting nine tungsten complexes have been determined from chemical equilibria and electrochemical data in MeCN solution (T = 22 °C). Homolytic W-H bond dissociation free energies are 59.3(3) kcal mol(-1) for CpW(CO)(2)(IMes)H and 59(1) kcal mol(-1) for the dihydride [CpW(CO)(2)(IMes)(H)(2)](+) (where IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), indicating that the bonds are the same within experimental uncertainty for the neutral hydride and the cationic dihydride. For the radical cation, [CpW(CO)(2)(IMes)H](•+), W-H bond homolysis to generate the 16-electron cation [CpW(CO)(2)(IMes)](+) is followed by MeCN uptake, with free energies for these steps being 51(1) and -16.9(5) kcal mol(-1), respectively. Based on these two steps, the free energy change for the net conversion of [CpW(CO)(2)(IMes)H](•+) to [CpW(CO)(2)(IMes)(MeCN)](+) in MeCN is 34(1) kcal mol(-1), indicating a much lower bond strength for the 17-electron radical cation of the metal hydride compared to the 18-electron hydride or dihydride. The pK(a) of CpW(CO)(2)(IMes)H in MeCN was determined to be 31.9(1), significantly higher than the 26.6 reported for the related phosphine complex, CpW(CO)(2)(PMe(3))H. This difference is attributed to the electron donor strength of IMes greatly exceeding that of PMe(3). The pK(a) values for [CpW(CO)(2)(IMes)H](•+) and [CpW(CO)(2)(IMes)(H)(2)](+) were determined to be 6.3(5) and 6.3(8), much closer to the pK(a) values reported for the PMe(3) analogues. The free energy of hydride abstraction from CpW(CO)(2)(IMes)H is 74(1) kcal mol(-1), and the resultant [CpW(CO)(2)(IMes)](+) cation is significantly stabilized by binding MeCN to form [CpW(CO)(2)(IMes)(MeCN)](+), giving an effective hydride donor ability of 57(1) kcal mol(-1) in MeCN. Electrochemical oxidation of [CpW(CO)(2)(IMes)](-) is fully reversible at all observed scan rates in cyclic voltammetry experiments (E° = -1.65 V vs Cp(2)Fe(+/0) in MeCN), whereas CpW(CO)(2)(IMes)H is reversibly oxidized (E° = -0.13(3) V) only at high scan rates (800 V s(-1)). For [CpW(CO)(2)(IMes)(MeCN)](+), high-pressure NMR experiments provide an estimate of ΔG° = 10.3(4) kcal mol(-1) for the displacement of MeCN by H(2) to give [CpW(CO)(2)(IMes)(H)(2)](+).
Communist History: An Annual Bibliography (2005)
The subject of this bibliography is the scholarly literature of communist history. For the USA coverage is extensive. For the rest of the Anglophone world coverage is selective, while coverage for the rest of the world is more selective still. Coverage of the former and presently communist countries is largely limited to works dealing with the Communist parties of those countries. Anti-communism is covered selectively, with somewhat more emphasis on its interaction with communism than its nature as a movement/ideology per se. Coverage of related topics, i.e. the labor movement, Marxism, other strains of radicalism, etc., is highly selective and limited to items directly relevant to communism. For coverage of current reportage (newspapers, news weeklies, journals of opinion, Internet/WWW discussion lists, etc.) see the Newsletter of the Historians of American Communism and the Historians of American Communism Discussion List (h-hoac@h-net.msu.edu). The Bibliography is organized into seven sections, listed below. Sections 1–5 are form and genre based (monographs, serials, etc.), while sections 6 and 7 are format based (sound and visual, electronic). Entries are arranged alphabetically within each section. Where the number of entries warrants it, a section is divided into USA and Other. There is no index. Please be aware that most citations for items in electronic format are listed under their appropriate form/genre, i.e. articles in electronic serials are listed under serials. Section 7 (Internet, WWW, etc.) only contains citations for items in forms and genres irreducibly unique to the electronic environment, i.e. discussion lists (and postings and threads therein) and for those web sites and other electronic resources not subsumed under categories 1–7. Items cited are from the calendar year in the title of the Bibliography, with two exceptions, Internet/WWW items, where publication/creation date information is often unavailable or indeterminate, and older items not cited