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Article

Synthesis and Structures of Dinuclear 3,5-Bis(trifluoromethyl)pyrazolate Complexes of Ruthenium

Supporting Info

Abdul Waheed^†, Richard A. Jones*^†, Kyriacos Agapiou^†, Xiaoping Yang^†, Jennifer A. Moore^† and John G. Ekerdt^‡

Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A 5300, Austin, Texas 78712-0165, and Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712

Organometallics, 2007, 26 (27), pp 6778–6783

DOI: 10.1021/om700521y

Publication Date (Web): December 5, 2007

* To whom correspondence should be addressed. E-mail: rajones@mail.utexas.edu., †

Department of Chemistry and Biochemistry, The University of Texas at Austin.

, ‡

Department of Chemical Engineering, The University of Texas at Austin.

Abstract

Reaction of 3,5-(CF₃)₂PzLi with [Cp*RuCl₂]_n (2:1) in diethyl ether at −78 °C gives [(Cp*RuLi)₂(μ₄-O)(μ₂-Cl)(μ-3,5-(CF₃)₂Pz)₃] (1) in 75% yield [3,5-(CF₃)₂Pz = 3,5-bis(trifluoromethyl)pyrazolate]. With a 1:1 ratio of [Cp*RuCl₂]_n to 3,5-(CF₃)₂PzLi, dark-green crystalline [Cp*Ru(μ-Cl)]₂(μ-3,5-(CF₃)₂Pz) (2) is produced in ca. 50% yield. The reaction of 3,5-(CF₃)₂PzLi with [RuCl₂(1,4-Me,iPrC₆H₄)]₂ in diethyl ether at −78 °C gives the chloride-bridged dimer [RuCl(η⁶-1,4-Me,iPrC₆H₄)(μ-3,5-(CF₃)₂Pz)]₂ (3) in 65% yield. The reaction of Cp*Ru(OSO₂CF₃)₂ with 3,5-(CF₃)₂PzLi (2:1) in diethyl ether at −78 °C produced the unusual dinuclear Ru^III−Ru^III complex [Cp*Ru(μ-O)(μ-η⁵,η¹-C₅Me₄CH₂)Ru(η¹-3,5-(CF₃)₂Pz)]·0.25Et₂O (4) in 75% yield. Complexes 1–4 have been characterized spectroscopically and by single-crystal X-ray diffraction studies.