Synthesis of benzene ruthenium triazolato complexes by [3+2] cycloaddition reactions of activated alkynes and fumaronitrile to benzene ruthenium azido complexes
Synthesis of benzene ruthenium triazolato complexes by [3+2] cycloaddition reactions of activated alkynes and fumaronitrile to benzene ruthenium azido complexes
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活化炔烃与富马腈的[3 2]环加成反应合成苯钌三唑配合物
DOI：
10.1016/j.ica.2007.05.063
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发表时间：
2008
影响因子：
2.8
通讯作者：
M. Kollipara
中科院分区：
文献类型：
--
作者：
K. Pachhunga;B. Therrien;M. Kollipara
[（η 6-C6 H6）Ru（μ-N3）Cl] 2与叠氮化钠在乙醇中反应得到双核配合物[（η6-C6 H6）Ru（μ-N3）Cl]2（1）。在甲醇中，[（η 6-C6 H6）RuCl 2] 2与相应的β-二酮反应，得到了通式为[（η 6-C6 H6）Ru（L <$L）Cl] {L <$L=O，O ′-acac（2）; O，O ′-bzac（3）; O，O′-dbzm（4）}的苯钌β-二酮配合物.这些配合物进一步与叠氮化钠在乙醇中反应，得到[（η6-C6 H6）Ru（L <$L）N3] [L <$L=O，O′-acac（5）; L <$L=O，O′-bzac（6）; L <$L=O，O′-dbzm（7）]型配合物。用β-二酮的钠盐处理化合物1也得到了配合物5-7。这些中性苯钌叠氮配合物与活化炔发生[3 +2]偶极环加成反应（MeO 2CCCCO 2 Me、EtO 2CCCCO 2 Et）或乙腈（NCHCCHCN），得到相应的苯钌三唑配合物;[（η6-C6H6）Ru]（O，O′-acac）{N3C2（CO2Me）2}]（8），[（η6-C6H6）Ru（O，O′-acac）{N3C2（CO2Et）2}]（9）、[（η6-C6H6）Ru（O，O′-acac）{N3C2HCN}]（10）、[（η6-C6H6）Ru（O，O′-bzac）{N3C2HCN}]（11）和[（η6-C6H6）Ru（O，O′-dbzm）{N3C2HCN}]（12）。这些配合物的充分特点的基础上，微量分析，FT-IR和FT-NMR光谱。[（η6-C6 H6）Ru（O，O′- acac）{N3 C2（CO2 C2 H5）2}]（9）的分子结构由单晶X射线衍射研究证实。
The dinuclear complex [(η6-C6H6)Ru(μ-N3)Cl]2(1) is obtained by the reaction of [(η6-C6H6)RuCl2]2with sodium azide in ethanol. The benzene ruthenium β-diketonato complexes of the general formula [(η6-C6H6)Ru(L∩L)Cl] {L∩L=O,O′-acac (2); O,O′-bzac (3); O,O′-dbzm (4)} are obtained in methanol by the reaction of [(η6-C6H6)RuCl2]2with the corresponding β-diketonates. These complexes further react with sodium azide in ethanol to yield complexes of the type [(η6-C6H6)Ru(L∩L)N3] [L∩L=O,O′-acac (5); L∩L=O,O′-bzac (6); L∩L=O,O′-dbzm (7)]. The complexes 5–7 are obtained as well by treating 1 with sodium salts of β-diketonates. These neutral benzene ruthenium azido complexes undergo [3+2] dipolar cycloaddition reaction with activated alkynes (MeO2CCCCO2Me, EtO2CCCCO2Et) or fumaronitrile (NCHCCHCN) to yield the corresponding benzene ruthenium triazolato complexes; [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Me)2}] (8), [(η6-C6H6)Ru(O,O′-acac){N3C2(CO2Et)2}] (9), [(η6-C6H6)Ru(O,O′-acac){N3C2HCN}] (10), [(η6-C6H6)Ru(O,O′-bzac){N3C2HCN}] (11) and [(η6-C6H6)Ru(O,O′-dbzm){N3C2HCN}] (12). These complexes are fully characterized on the basis of microanalyses, FT-IR and FT-NMR spectroscopy. The molecular structure of [(η6-C6H6)Ru(O,O′- acac){N3C2(CO2C2H5)2}] (9) is confirmed by single crystal X-ray diffraction study.