4.4 Review

Sixty-Year Saga (1952-2013) of the Solid-State Structure of Triiron Dodecacarbonyl

Journal

JOURNAL OF CLUSTER SCIENCE
Volume 25, Issue 1, Pages 205-224

Publisher

SPRINGER/PLENUM PUBLISHERS
DOI: 10.1007/s10876-013-0667-z

Keywords

Triiron dodecacarbonyl; X-ray crystal structure; Dynamic behavior

Funding

  1. UW-Madison Graduate School
  2. Chemistry Department

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This article presents the personal saga of one of the authors (LFD) in the determination of the solid-state structure of Fe-3(CO)(12). We also present the results of our recent determination of its solid-state structure at low temperature (100 K), in which we have used a modern area-detector diffractometer in order to examine more precisely its temperature-dependent structural variations reported by Braga et al. in 1994 from a point-detector diffractometer. These investigations provide a striking illustration of the remarkable advances over the last six decades in both computational hardware and software packages as well as the recent improvements in hardware data-collection instrumentation that have given rise to X-ray crystallography now being the most powerful (and in most cases the only unambiguous) physical method for elucidating the static structures of complex metal clusters. Other experimental measurements and resulting speculations concerning the dynamic/fluxional behavior of Fe-3(CO)(12) and closely related analogues in the solid state and in solution are briefly mentioned, as are recent theoretical analyses.

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