Not So Inert

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Science  19 Aug 2005:
Vol. 309, Issue 5738, pp. 1157
DOI: 10.1126/science.309.5738.1157b

Sulfur hexafluoride (SF6) is so unreactive that it can be used, among other applications, as a protective blanket for processing highly reactive magnesium metal, yet its long lifetime in the atmosphere (>3000 years) has caused concern because it has the strongest greenhouse effect known for any gas. Despite the reputation of SF6 for inertness, Basta et al. report a reaction in which it proves to be a faster fluorinating agent than normally more reactive compounds such as XeF2 or CoF3. The low-valent Ti compound, Ti[1,3-C5H3(tert-C4H9)2](6,6-dimethylcyclohexadienyl)(P(CH3)3), which can be regarded as a half-open titanocene, reacted readily with SF6 to produce the tetrameric product {Ti[1,3-C5H3(tert-C4H9)2]F2}4 and the byproduct (CH3)3PS. The authors propose that SF6 can coordinate an F atom to the metal center and drive the reaction through an oxidative inner-sphere electron transfer. — PDS

J. Am. Chem. Soc. 10.1021/ja052214s (2005).

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