SYNTHESIS AND X-RAY CRYSTALLOGRAPHIC CHARACTERIZATION OF AN OXO-BRIDGED BIMETALLIC ORGANOSAMARIUM COMPLEX, [(C5ME5)2SM]2(MU-O)
SYNTHESIS AND X-RAY CRYSTALLOGRAPHIC CHARACTERIZATION OF AN OXO-BRIDGED BIMETALLIC ORGANOSAMARIUM COMPLEX, [(C5ME5)2SM]2(MU-O)
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DOI：
10.1021/ja00288a021
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发表时间：
1985-01-01
影响因子：
15
通讯作者：
ATWOOD, JL
中科院分区：
文献类型：
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作者：
EVANS, WJ;GRATE, JW;ATWOOD, JL
[(C5Me5) 2Sm] 2^-0) 是 (C5Me5) 2Sm (THF) 2 与含氧底物（例如 NO、N2O、CH3CH2CHCH20 或 C5H5NO）反应中的常见产物。环氧化物反应释放副产物 CH3CH2CH= CH2，产率最高，为 55%。[(C5Me5) 2Sm] 2^-0) 在戊烷扩散下在 3 C 下从甲苯/己烷中结晶，空间群为 742m，晶胞尺寸 a= 11.560 (5) Á、c= 14.236 (6) Á、Z= 2 （二聚体）Dc= 1.50 g cm'3。基于 962 个观察到的反射的最小二乘细化得出最终 R 值为 0.036。二聚体的两个 (C5Me5) 2Sm 单元通过线性 Sm-O-Sm 桥连接，Sm-O 距离为 2.094 (1) µ。四个 C5Me5 环的质心定义了一个围绕 Sm-O-Sm 单元的四面体。每个钐上的 C5Me5 环都呈重叠构象。与上述氧化反应相反，(C5Me5) 2Sm (THF) 2 与OP (CfiH<) 3 反应形成二价加合物(C5Me5) 2Sm [OP (C6H5) 3](THF)。
[(C5Me5) 2Sm] 2^-0) is a common product in reactions of (C5Me5) 2Sm (THF) 2 with oxygen-containing substrates such as NO, N20, CH3CH2CHCH20, or C5H5NO. The epoxide reaction, which liberates CH3CH2CH= CH2 as a byproduct, gives the best yield, 55%.[(C5Me5) 2Sm] 2^-0) crystallizes from toluene/hexaneunder pentane diffusion at-3 C in space group 742m with unit cell dimensions a= 11.560 (5) Á, c= 14.236 (6) Á, and Z= 2 (dimers) for Dc= 1.50 g cm'3. Least-squares refinement on the basis of 962 observed reflections led to a final Rvalue of 0.036. The two (C5Me5) 2Sm units of the dimer are connected by a linear Sm-O-Sm bridge withSm-O distances of 2.094 (1) Á. The centroids of the four C5Me5 rings define a tetrahedron which surrounds the Sm-O-Sm unit. The C5Me5 rings are in an eclipsed conformation on each samarium. In contrast to the above oxidation reactions,(C5Me5) 2Sm (THF) 2 reacts with OP (CfiH<) 3 to form the divalent adduct (C5Me5) 2Sm [OP (C6H5) 3](THF).