Some Ruthenium Derivatives of Penta-1,4-diyn-3-one
Some Ruthenium Derivatives of Penta-1,4-diyn-3-one
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DOI：
10.1021/om400208q
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发表时间：
2013-05
期刊：
影响因子：
2.8
通讯作者：
M. Bruce;Aléxandre Burgun;M. A. Fox;M. Jevric;P. Low;B. K. Nicholson;C. R. Parker;B. Skelton
中科院分区：
文献类型：
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作者：
M. Bruce;Aléxandre Burgun;M. A. Fox;M. Jevric;P. Low;B. K. Nicholson;C. R. Parker;B. Skelton
Ru(C=CH)(dppe)Cp* (1) 和草酰氯之间的反应得到 ({Ru(dppe)Cp*}C=C)2CO (2)，产率 72%。 2 的甲基化 (MeOTf) 首先发生在羰基氧上，得到 [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf)。 [3]+ 在炔基 Cβ 上的第二次甲基化缓慢进行，得到 [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([4][OTf]2)，而 [3]+ 的质子化很容易产生晶体学特征[{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([5][OTf]2)。 [3]OTf 和 [5][OTf]2 的分子结构表明，CO 基团的极化分别导致炔基-亚烯基或炔基-碳炔介晶体的显着贡献。 2 在含有 [NH4]PF6 的回流 MeOH 中反应，导致部分甲醇分解，得到 Ru{C≡CC(O)CH=CH(OMe)}(dppe)Cp* (6)。 2 与 CH2(CN)2 的诺维格尔缩合得到 {[Ru(dppe)Cp*]C≡C}2C=C(CN)2 (7)。相关的不对称配合物 {Cp*(dppe)Ru}C−C[C=C(CN)2]C−CC−C{Ru(dppe)Cp*} (8) 是从 r...
The reaction between Ru(C≡CH)(dppe)Cp* (1) and oxalyl chloride affords ({Ru(dppe)Cp*}C≡C)2CO (2) in 72% yield. Methylation (MeOTf) of 2 occurs first on the carbonyl oxygen, affording [({Ru(dppe)Cp*}C≡C)2C(OMe)]OTf ([3]OTf). A second methylation of [3]+ on the alkynyl Cβ proceeds slowly, affording [{Cp*(dppe)Ru}CCMeC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([4][OTf]2), whereas protonation of [3]+ occurs readily to give crystallographically characterized [{Cp*(dppe)Ru}CCHC(OMe)CC{Ru(dppe)Cp*}][OTf]2 ([5][OTf]2). The molecular structures of [3]OTf and [5][OTf]2 suggest that polarization by the CO group results in significant contributions from the alkynyl-allenylidene or alkynyl-carbyne mesomers, respectively. Reaction of 2 in refluxing MeOH containing [NH4]PF6 results in partial methanolysis to give Ru{C≡CC(O)CH═CH(OMe)}(dppe)Cp* (6). Knovenagel condensation of 2 with CH2(CN)2 affords {[Ru(dppe)Cp*]C≡C}2C═C(CN)2 (7). The related asymmetric complex {Cp*(dppe)Ru}C≡C[C═C(CN)2]C≡CC≡C{Ru(dppe)Cp*} (8) was obtained from the r...