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Inorg Chem. 2013 Sep 16;52(18):10449-55. doi: 10.1021/ic401289k. Epub 2013 Sep 6.

Facile η5-η1 ring slippage of the cycloolefin ligands in osmocene and bis(η5-indenyl)ruthenium(II).

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  • 1Department of Chemistry, The Hong Kong University of Science and Technology , Clear Water Bay, Kowloon, Hong Kong, People's Republic of China.

Abstract

η(5)-η(1) ring slippage of [OsCp2] (Cp = η(5)-C5H5) and [Ru(η(5)-ind)2] (ind = indenyl) resulting from reaction with the ruthenium(VI) nitride [Ru(L(OEt))(N)Cl2] (1; L(OEt)(-) = [CoCp{P(O)(OEt)2}3](-)) is reported. The treatment of [OsCp2] or [Ru(η(5)-ind)2] with 1 resulted in η(5)-η(1) ring slippage of the cycloolefin ligands and formation of the trinuclear nitrido complexes [Cp(η(1)-C5H5)Os(NRuL(OEt)Cl2)2] (2) or [(η(5)-ind)(η(1)-ind)Ru(NRuL(OEt)Cl2)2] (3). No reactions were found between [OsCp2] and amines, such as pyridine and 2,2'-bipyridyl, or other metal nitrides, such as [Os(L(OEt))(N)Cl2], indicating that the electrophilic property of 1 is essential for ring slippage. The crystal structures of 2 and 3 have been determined. The short Os-N distances in 2 [1.833(5) and 1.817(5) Å] and the (ind)Ru-N distances in 3 [1.827(5) and 1.852(5) Å] are indicative of multiple bond character, consistent with density functional theory (DFT) calculations. Therefore, 2 and 3 may be described by two resonance forms: Ru(VI)-M(II)-Ru(VI) and Ru(IV)-M(VI)-Ru(IV) (M = Os, Ru). Also, DFT calculations indicate that for the reaction of 1 with [OsCp2] or [Ru(η(5)-ind)2], η(5)-η(1) ring slippage is energetically more favorable than the η(5)-η(3) counterpart. The driving force for η(5)-η(1) ring slippage is believed to be the formation of the strong M-N (M = Os, Ru) (multiple) bonds. By contrast, the same reaction with acetonitrile is energetically uphill, and thus no ring slippage occurs.

PMID:
24007355
[PubMed]
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