[Os(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)<sub>2</sub>]: A carbon-free analog of ferrocene.
basic_science · Level V
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- Record sourced from PubMed, PMID 42024744.
- Also identified by DOI 10.1126/science.aed9192.
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Abstract
The synthesis of a carbon-free analog of ferrocene has been a long-standing goal in inorganic chemistry. We report here the preparation and crystallographic characterization of the carbon-free sandwich complex [Os(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)<sub>2</sub>], which is qualitatively similar to ferrocene in structure and bonding. The metal-ring bonding is much stronger in [Os(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)<sub>2</sub>], owing to rehybridization of the π molecular orbitals brought in by the bridging B-H-B hydrogens and the bent B-H<sub>t</sub> bonds of the larger B<sub>5</sub>H<sub>10</sub> ring (where B-H<sub>t</sub> is the terminal B-H bond). This also leads to an unusually short ring-ring separation of 3.071 angstroms and a staggered conformation. The isomeric [Os(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)(η<sup>3</sup>-B<sub>5</sub>H<sub>10</sub>)], which features a coordination mode unknown for ferrocene, has also been isolated. A similar attempt for [Ru(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)<sub>2</sub>] resulted only in [Ru(η<sup>5</sup>-B<sub>5</sub>H<sub>10</sub>)(η<sup>3</sup>-B<sub>5</sub>H<sub>10</sub>)].