Rhodium(I) Complexes of the Conformationally Rigid IBioxMe4 Ligand: Preparation of Mono-, Bis-, and Tris-ligated NHC Complexes

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• 作者：Adrian B. Chaplin
• 刊名：Organometallics
• 出版年：2014
• 出版时间：June 23, 2014
• 年：2014
• 卷：33
• 期：12
• 页码：3069-3077
• 全文大小：491K
• ISSN：1520-6041

文摘

The preparation and characterization of a series of mono-, bis-, and tris-ligated rhodium(I) complexes of Glorius鈥?conformationally rigid bioxazoline-derived N-heterocyclic carbene ligand IBioxMeb>4b> are described. Through reaction of [Rh(COE)b>2b>Cl]b>2b> (COE = cis-cyclooctene) with isolated IBioxMeb>4b>, [Rh(IBioxMeb>4b>)(COE)Cl]b>2b> (<b>1b>), trans-[Rh(IBioxMeb>4b>)b>2b>(COE)Cl] (<b>2b>), and [Rh(IBioxMeb>4b>)b>3b>Cl] (<b>3b>) were each isolated by careful choice of the reaction conditions. Further substitution and salt metathesis reactions of <b>1b>鈥?b>3b> were investigated, and derivatives containing CO, norbornadiene, and cyclopentadienyl ancillary ligands were readily isolated. Notably, halide abstraction from <b>2b> and <b>3b> using Na[BAr^Fb>4b>] (Ar^F = 3,5-Cb>6b>Hb>3b>(CFb>3b>)b>2b>) resulted in the formation of low-coordinate T-shaped cis-[Rh(IBioxMeb>4b>)b>2b>(COE)][BAr^Fb>4b>] (<b>9b>) and [Rh(IBioxMeb>4b>)b>3b>][BAr^Fb>4b>] (<b>11b>). The solid-state structures of <b>2b>, <b>9b>, and <b>11b> each feature IBioxMeb>4b> ligands that bind unusually with tilted coordination geometries.