Transformations of Alkynes at a Cyclotriphosphato Ruthenium Complex

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• 作者：Keiichiro Kanao ; Yousuke Ikeda ; Kazuhiro Kimura ; Sou Kamimura ; Yoshiaki Tanabe ; Yuichiro Mutoh ; Masakazu Iwasaki ; Youichi Ishii
• 刊名：Organometallics
• 出版年：2013
• 出版时间：January 28, 2013
• 年：2013
• 卷：32
• 期：2
• 页码：527-537
• 全文大小：565K
• 年卷期：v.32,no.2(January 28, 2013)
• ISSN：1520-6041

文摘

Photolysis of the cyclotriphosphato complex (PPN)[Ru(P₃O₉)(畏⁶-C₆H₆)] (2) with bpy (2,2鈥?bipyridyl) in alcohols generated a violet solution of (PPN)[Ru(P₃O₉)(bpy)(ROH)] (3) with a labile alcohol ligand. Complexes 3 were readily oxidized during recrystallization to give the Ru(III) alkoxo complexes (PPN)[Ru(OR)(P₃O₉)(bpy)] (4). Treatment of 3 with internal alkynes led to selective formation of 畏²-alkyne complexes (PPN)[Ru(P₃O₉)(bpy)(畏²-RC鈮R鈥?] (7), which did not undergo vinylidene rearrangement under heating and photoirradiation conditions in contrast to its dppe analogues. On the other hand, diphenylacetylene complex 7c (R = R鈥?= Ph) gave the 伪-ketocarbene complex (PPN)[Ru(P₃O₉)(bpy)(鈺怌PhCOPh)] (8) on reaction with m-CPBA. This observation provides a very rare example for the direct and controlled oxidation of a coordinated alkyne ligand. Reactions of 3 with the terminal alkynes in alcohols and in DMF afforded the alkoxycarbene complexes (PPN)[Ru(P₃O₉)(bpy){鈺怌(OR)CH₂CR鈥瞹] (9) and the carbonyl complex (PPN)[Ru(P₃O₉)(CO)(bpy)] (12), respectively, presumably by way of vinylidene intermediates.