Preparation and structural characterization of three tetracarboxylato dirhodium (RhRh) compounds with bulky ligands
Preparation and structural characterization of three tetracarboxylato dirhodium (RhRh) compounds with bulky ligands
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三种大配体四羧酸二铑 (RhRh) 化合物的制备和结构表征
DOI：
10.1016/s0020-1693(00)88758-7
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发表时间：
1984
影响因子：
2.8
通讯作者：
J.Lon Thompson
中科院分区：
文献类型：
--
作者：
F. Cotton;J.Lon Thompson
本文报道了三种化合物的合成和结构：红紫色Rh 2 [O2 C（2-C6 H5）C6 H4]4（CH 3CN）2·3C 6 H6（1），浅蓝色Rh 2 [O2 C（1-金刚烷基）]4（CH 3OH）2·5CH 3OH（2），红紫色Rh 2（O2 CCH 3）2（O2 CCPh 3）2（CH 3CN）2·C6 H5 CH 3（3）。化合物1在三斜晶系中从苯/乙腈混合物中结晶，其中掺入苯，晶胞尺寸为a = 13.469（1）°，B=13.507（2）°，c= 9.908（1）°，α = 110.44（1）°，β = 92.78（1）°，γ = 107.92（1）°，V= 1582（3）° 3和Z = 1。邻苯基中的两个位于赤道区域，而另外两个朝向分子的每一端。轴向CH 3CN基团是紧密配位的（Rh <$N = 2.233（3）<$，Rh <$Rh <$N <$178 °），Rh <$Rh距离为2.396（1）<$。化合物2在正交晶系中从甲醇中结晶，晶胞参数a = 10.587（2）nm，B= 20.640（2）nm，c= 24.693（2）nm，V= 5396（2）nm 3，Z = 4。Rh <$Rh键长为2.371（2）<$，与已知的Rh_2（O_2CR）_4L_2化合物中最短的键长相等。对于化合物3，从乙腈-甲苯混合溶剂中生长晶体，并将甲苯分子引入三斜晶胞中，其尺寸为a = 12.664（1）°，B= 21.876（2）°，c= 9.686（2）°，α = 99.00（1）°，β = 105.27（1）°，γ = 75.61（1）°，V= 2496（1）° 3，Z = 2。Ph 3CCO 2配体是相互顺式的。Rh <$Rh和两个独立的Rh <$N距离分别为2.388（2）<$，2.21（1）<$和2.17（1）<$。
The preparation and structures of three compounds, red-purple Rh2[O2C(2-C6H5)C6H4]4(CH3CN)2·3C6H6(1), light blue Rh2[O2C(1-adamantyl)]4(CH3OH)2·5CH3OH (2), and red-purple Rh2(O2CCH3)2(O2CCPh3)2(CH3CN)2·C6H5CH3(3) are reported. Compound1crystallizes from a benzene/acetonitrile mixture, with benzene incorporated, in the triclinic system with a unit cell of dimensionsa= 13.469(1)Å,b=13.507(2)Å,c= 9.908(1)Å, α = 110.44(1)°, β = 92.78(1)°, γ = 107.92(1)°,V= 1582(3)Å3andZ= 1. Two of theo-phenyl groups are positioned in the equatorial region while the other two are oriented one towards each end of the molecule. The axial CH3CN groups are tightly coordinated (RhN = 2.233(3)Å, RhRhN ≈ 178°) and the RhRh distance is 2.396(1)Å. Compound2was crystallized from methanol in the orthorhomic system with unit cell dimensionsa= 10.587(2)Å,b= 20.640(2)Å,c= 24.693(2)Å,V= 5396(2)Å3andZ= 4. The RhRh bond length, 2.371(2)Å, is equal to the shortest one known in Rh2(O2CR)4L2compounds. For compound3crystals were grown from a mixed acetonitriletoluene solvent and incorporate toluene molecules in a triclinic unit cell of dimensionsa= 12.664(1)Å,b= 21.876(2)Å,c= 9.686(2)Å, α = 99.00(1)°, β = 105.27(1)°, γ = 75.61(1)°,V= 2496(1)Å3withZ= 2. The Ph3CCO2ligands are mutuallycis. The RhRh and two independent RhN distances are 2.388(2)Å, 2.21(1)Åand 2.17(1)Å.