School of Chemistry & Physics, University of Adelaide, Adelaide, South Australia 5005.
Dalton Trans. 2010 Apr 21;39(15):3759-70. doi: 10.1039/b921324d. Epub 2010 Mar 11.
In the eta(3)-butadienyl complex Ru{eta(3)-C(CN)(2)CPhC=C(CN)(2)}(PPh(3))Cp 1, which is formed from Ru(C[triple bond]CPh)(PPh(3))(2)Cp and tcne, a CN group reacts with MeO(-) to give the methoxy-amide Ru{NH=C(OMe)C(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 2, in which the NH has displaced the C=C from the Ru centre with formation of a RuC(3)N ring. "Click addition" of azide to a CN group in 1 gives the oligomeric tetrazolato complex Ru{N(3)N[Na(OEt(2))]=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 3, also containing a RuC(3)N ring. Salt-elimination reactions of 3 with MeOTf, FeCl(dppe)Cp, RuCl(dppe)Cp* and trans-PtCl(2){P(tol)(3)}(2) result in selective substitution at one nitrogen atom of the RuC(3)N ring. Geometries of 1 and the anion in 3 were computed by DFT methods. Preferences for CN groups attacked in the nucleophilic and cycloaddition reactions of 1 are supported by NBO calculations. Alkylation of 1 in reactions with 1,2-dimethoxyethane gave two isomers of Ru{N(3)[CH(CH(2)OMe)(OMe)]N=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 8 and 9, differing in the sites of attachment of the alkyl group, likely by radical processes. The molecular structures of eight complexes are reported, including a re-determination of 1. Computed NMR chemical shifts are used to reassign the butadienyl carbon resonances in the (13)C NMR spectrum of 1.
在 eta(3)-丁二烯基配合物 Ru{eta(3)-C(CN)(2)CPhC=C(CN)(2)}(PPh(3))Cp 1 中，该配合物由 Ru(C[三重键]CPh)(PPh(3))(2)Cp 和 tcne 形成，一个 CN 基团与 MeO(-)反应生成甲氧基酰胺 Ru{NH=C(OMe)C(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 2，其中 NH 取代了 Ru 中心的 C=C，形成了一个 RuC(3)N 环。在 1 中，叠氮化物与 CN 基团的“点击加成”反应得到了包含 RuC(3)N 环的聚合四唑配合物 Ru{N(3)N[Na(OEt(2))]=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 3。3 与 MeOTf、FeCl(dppe)Cp、RuCl(dppe)Cp*和 trans-PtCl(2){P(tol)(3)}(2)的盐消除反应导致 RuC(3)N 环上一个氮原子的选择性取代。通过 DFT 方法计算了 1 的结构和 3 中阴离子的结构。NBO 计算支持亲核和环加成反应中 CN 基团被攻击的偏好性。1 与 1,2-二甲氧基乙烷的反应中的烷基化得到了 Ru{N(3)[CH(CH(2)OMe)(OMe)]N=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 8 和 9 的两种异构体，它们的烷基连接点不同，可能是通过自由基过程。报道了包括 1 的重新测定在内的八个配合物的分子结构。计算的 NMR 化学位移用于重新分配 1 的 13C NMR 谱中的丁二烯碳共振。
