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CHEMISTRY HIGHLIGHTS 2002
December 16, 2002
Volume 80, Number 50
CENEAR 80 50 pp. 42-43
ISSN 0009-2347


INORGANIC CHEMISTRY

STU BORMAN, C&EN WASHINGTON

DOUBLE HELIX In structure synthesized by Gladysz and coworkers, two methylene chains wind around rodlike chain of carbon atoms like vines around a beanpole.
Two long-sought chain molecules of theoretical interest were prepared and positively identified this year (C&EN, Jan. 21, page 36). N4 was produced mass spectrometrically by Fulvio Cacace, Giulia de Petris, and Anna Troiani at the University of Rome, in Italy [Science, 295, 480 (2002)]. And Anders Engdahl and Bengt Nelander of Lund University, in Sweden, made H2O3 by laser irradiation [Science, 295, 482 (2002)]. According to Cacace, the studies exemplify an emerging theme: the synthesis of simple inorganic molecules containing first-period main-group atoms.

Bruce E. Bursten of Ohio State University, Lester Andrews of the University of Virginia, and coworkers discovered the first noble gas-actinide complexes--in which argon, krypton, and xenon interact with the uranium atom in CUO [Science, 295, 2242 (2002); J. Am. Chem. Soc., 124, 9016 (2002); C&EN, March 4, page 35].

A team led by Guy Bertrand of UC Riverside and CNRS (the French National Center for Scientific Research) designed a singlet diradical that is stable at room temperature for months [Science, 295, 1880 (2002); C&EN, March 11, page 12]. It's a planar, four-membered ring compound with alternating phosphorus and boron groups (below). Superconducting or magnetic applications are possible.

Sodium nitride, a compound some scientists believed could not exist, was synthesized and characterized by Dieter Fischer and Martin Jansen at Max Planck Institute for Solid-State Research, Stuttgart, Germany [Angew. Chem. Int. Ed., 41, 1755 (2002); C&EN, May 20, page 9]. Their synthetic technique may be applicable to the preparation of binary nitrides of other alkali metals.

Definitive evidence for the long-sought free silylium ion (R3Si+, where R is an aryl group) was obtained for the first time by Christopher A. Reed at UC Riverside, Joseph B. Lambert at Northwestern, and coworkers [Science, 297, 825 (2002); C&EN, Aug. 5, page 25].

John L. Marshall and Stephen J. Telfer and coworkers at Polaroid, Waltham, Mass., developed an imaging system consisting of photoacid-generating and dye layers on a substrate as a potential alternative to conventional silver halide-based photographic film [Science, 297, 1516 (2002); C&EN, Aug. 12, page 11].

A stable molecule with an ionization energy about 10% lower than that of any other known stable atom or molecule was identified by F. Albert Cotton and Carlos A. Murillo of Texas A&M University; Jiande Gu of the Shanghai Institute of Materia Medica, China; Dennis L. Lichtenberger of the University of Arizona, Tucson; and coworkers [Science, 298, 1971 (2002); C&EN, Dec. 9, page 6]. The molecule and analogs represent a new class of powerful reductants for chemical reactions and other uses.

And a novel class of double-helical molecules with potential molecular electronics applications was synthesized by John A. Gladysz at the University of Erlangen-Nuremberg, Germany, and coworkers [Angew. Chem. Int. Ed., 41, 1871 (2002); C&EN, June 3, page 7]. In the molecules, two platinum atoms are bridged by a chain of triply-bonded carbons, along which electrons and charge can flow, and are surrounded by diphosphine ligands bearing an insulating methylene double helix. "We are now entering an era where synthetic inorganic and organometallic chemists have developed a sufficient body of 'reliable' reactions that multistage syntheses of sophisticated targets are increasingly possible," Gladysz tells C&EN.

 



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