Interconversion of Ruthenium-O(CH2CH2PCy2)2 Alkylidene and Alkylidyne Hydride Complexes

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• 作者：Michael P. Boone ; Christopher C. Brown ; Travis A. Ancelet ; Douglas W. Stephan
• 刊名：Organometallics
• 出版年：2010
• 出版时间：October 11, 2010
• 年：2010
• 卷：29
• 期：19
• 页码：4369-4374
• 全文大小：794K
• 年卷期：v.29,no.19(October 11, 2010)
• ISSN：1520-6041

文摘

The species (Cy₃P)₂RuX₂(CHPh) (X = Cl, Br) react with the ancillary ligand O(CH₂CH₂PCy₂)₂ to yield the alkylidene species (POP-Cy)RuX₂(CHPh) (X = Cl 1, Br 2). Subsequent reaction of 1 and 2 with GaX₃ generates the alkylidyne hydride salts [(POP-Cy)RuHX(CPh)][GaX₄] (X = Cl 3, Br 4). Treatment of 3 and 4 with the donor ligand pyridine converts these alkylidyne hydrides to the Ru-alkylidene complexes [(POP-Cy)Ru(py)X(CHPh)][GaX₄] (X = Cl 5, Br 6). The complexes 5 and 6 are also formed directly by addition of the Lewis acid−base adduct (py)GaX₃ to 1 and 2, respectively. The alkylidyne hydride species 3 and 4 are also quantitatively converted back to alkylidene species 1 and 2 by addition of excess Bu₄NX (X = Cl, Br), respectively. Similarly treatment of 5 and 6 with [Et₃NH]X or [Bu₄N]X (X = Cl, Br) resulted in the re-formation of 1 and 2. These data demonstrate that the interconversion of alkylidene and alkylidyne hydride is energetically facile. This view is supported by crystallographic and preliminary DFT data.