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Article Captures PNAS Cover

The Journal PNAS, Proceedings of the National Academy of Sciences of the United States, devoted its April 24th, 2007 cover to a perspective article on dihydrogen coordination chemistry. The article was written by Dr. Gregory Kubas of Chemistry Division, who is credited with the discovery of dihydrogen complexes.

The binding of a dihydrogen molecule (H2) to a transition metal center in an organometallic complex was a major discovery because it changed the way chemists think about the reactivity of molecules with chemically "inert" strong bonds such as HH and CH. Before the seminal finding of side-on bonded H2 in W(CO)3(PR3)2(H2), it was generally believed that H2 could not bind to another atom in stable fashion and would split into two separate H atoms to form a metal dihydride before undergoing chemical reaction. Metal-bound saturated molecules such as H2, silanes, and alkanes (sigma complexes) have a chemistry of their own, with surprisingly varied structures, bonding, and dynamics. H2 complexes are of increased relevance for H2 production and storage in the hydrogen economy of the future.

The article can be read at http://www.pnas.org/cgi/content/short/104/17/6901


PNAS

Cover image: the structure of dihydrogen (yellow) bound to tungsten in W(H2)(CO)3[P(i-C3H7)3]2 (gray, C; red, O; magenta, P). Determined in 1984 by Kubas et al., this was the first well-defined example of a stable three-center "sigma complex," the first step in breaking strong bonds such as H-H and C-H (lower equation). Center image by Gregory Kubas, Brian Scott, and Josh Smith (Los Alamos National Laboratory).

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