Cyclometallation of 2-(2-pyridyl)benzo[b]furan and1-(2-pyridyl and 2-pyrimidyl)indole with palladium(II)and rhodium(III). Structures of unexpectedly formed nitropalladium(II) complexes
Cyclometallation of 2-(2-pyridyl)benzo[b]furan and1-(2-pyridyl and 2-pyrimidyl)indole with palladium(II)and rhodium(III). Structures of unexpectedly formed nitropalladium(II) complexes
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2-(2-吡啶基)苯并[b]呋喃和1-(2-吡啶基和2-嘧啶基)吲哚与钯(II)和铑(III)的环金属化。
DOI：
10.1016/s0277-5387(98)00329-5
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发表时间：
1998
期刊：
影响因子：
2.6
通讯作者：
K. Nakajima
中科院分区：
文献类型：
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作者：
M. Nonoyama;K. Nakajima
2-（2-吡啶基）苯并[B]呋喃（Hpbf）、1-（2-吡啶基）吲哚（Hpyi）和1-（2-嘧啶基）吲哚（Hpmi）与乙酸钯（II）在乙腈中反应，生成了意想不到的硝基配合物[Pd（NO 2）L（CH 3 CN）]（L=pbf，pyi和pmi）.通过X-射线衍射分析证实了平面正方形二甲基亚砜（dmso）衍生物[Pd（NO2）L（dmso）]（L=pbf和pyi）中NO2的存在。pbf的C-3和pyi、pmi的C-2发生钯化，形成五元钯配体。NO2以反式配位到吡啶-N原子上，dmso通过O原子反式配位到C原子上。Hpbf、Hpyi和Hpmi分别与三氯双（三丁基膦）铑（III）在甲苯中进行环化反应，得到八面体配合物[RhCl_2L（PBu_3）_2]（PBu_3 =三丁基膦）。[RhCl_2（pmi）（PBu_3）_2]的八面体结构也通过X射线分析确定。两个PBu 3配体以反式相互配位，σ-C给体原子的强烈反式作用使一个Rh-Cl键反式伸展到它上面。
Reactions of 2-(2-pyridyl)benzo[b]furan (Hpbf), 1-(2-pyridyl)indole(Hpyi) and 1-(2-pyrimidyl)indole (Hpmi) with palladium(II) acetate in refluxing acetonitrile resulted in the formation of unexpected nitro complexes, [Pd(NO2)L(CH3CN)](L=pbf, pyi and pmi). The presence of NO2in the square planar dimethylsulfoxide(dmso) derivatives, [Pd(NO2)L(dmso)] (L=pbf and pyi) were confirmed by X-ray analysis. Palladation occurred at the C-3 of pbf and at the C-2 of pyi and pmi and a five member palladacycle was formed. The NO2was coordinated trans to the pyridine-N atom and the dmso trans to the C atom through the O atom. Cyclorhodation of Hpbf, Hpyi and Hpmi with trichlorobis(tri-n-butylphosphine)rhodium(III) were similarly occurred inrefluxing toluene to afford octahedral complexes, [RhCl2L(PBu3)2],(PBu3=tri-n-butylphosphine). The octahedral structure of [RhCl2(pmi)(PBu3)2] was also determined by X-ray analysis. The two PBu3ligands were coordinated trans to each other and the strong trans influence of the σ-C donor atom stretched one Rh–Cl bond trans to it.
DOI：
--
发表时间：
2003
期刊：
影响因子：
--
作者：
T.Nishigaki et al.;S.Itoh.et al.
通讯作者：
S.Itoh.et al.