COORDINATION AND TRANSFORMATIONS OF BENZOTHIENYL LIGANDS BY TRIOSMIUM CLUSTER COMPLEXES
COORDINATION AND TRANSFORMATIONS OF BENZOTHIENYL LIGANDS BY TRIOSMIUM CLUSTER COMPLEXES
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DOI：
10.1021/om00005a025
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发表时间：
1995-05-01
期刊：
影响因子：
2.8
通讯作者：
QU, XS
中科院分区：
文献类型：
--
作者：
ADAMS, RD;QU, XS
本文研究了苯并噻吩和1-溴苯并噻吩与Os-3（CO）（10）（NCMe）（2）的反应。在25 ℃下，苯并噻吩与Os-3（CO）（10）（NCMe）（2）反应，得到两种产物Os-3（CO）（10）（mu-SCCHC_6 H_5）（mu-H），1（10%）和Os-3（CO）（9）（mu-SCCC_6 H_5）（mu-H）（2），2（8%）.通过单晶X射线衍射分析对两种产物进行了表征。两种产品都含有苯并噻吩配体，分别通过苯并噻吩分子的一个和两个C-H键的活化而转化。化合物1由闭合的三锇簇组成，其中μ（3）-η（2）-苯并噻吩基配体通过配体的五元环中的C-C双键配位到簇的边缘。化合物2含有与闭合的三锇簇合物的表面配位的μ（3）-η（2）-苯并噻吩配体。化合物1通过在辛烷溶剂中加热至125 ℃转化为2，产率为80%。1-溴苯并噻吩与Os-3（CO）（10）（NCMe）（2）在25 ℃反应，得到两种产物：Os-3（CO）（10）（mu-SCCHC 6 H5）（mu-Br），3（32%）和Os-3（CO）（9）（mu-SCCHC 6 H5）（mu-Br），4（10%）。这两种产物都含有通过将溴苯并噻吩的C-Br键氧化加成到簇上而形成的苯并噻吩基配体。在3中，苯并噻吩基配体通过硫和相邻的碳原子配位在开放的三锇簇的开放边缘上。在4中，苯并噻吩基配体是使用硫原子和五元环的C-C双键的三重桥接配体。通过在庚烷溶剂中加热至97 ℃ 30分钟，将化合物3以74%产率转化为4。空间群= P2（1）/n，a = 7.668（2）埃，B = 31.464（5）埃，c = 9.452（2）埃，β = 105.48（2）度，Z = 4，2563次反射，R = 0.035。晶体数据为2：空间群= P1 $（$）/棒$$，a = 9.791（1）埃，B = 14.576（2）埃，c = 8.094（1）埃，α = 95.44（1）度，β = 107.47（1）度，γ = 95.23（1）度，Z = 2，2218次反射，R = 0.024。3的晶体数据：空间群= P2（1）/c，a = 9.116（2）埃，B = 15.577（3）埃，c = 16.270（3）埃，β = 100.16（1）度，Z = 4，2193次反射，R = 0.038。4的水晶数据：空间群= P2（1）/n，a = 7.796（1）埃，B = 15.543（3）埃，c = 17.640（2）埃，β = 90.48（1）度，Z = 4，2288次反射，R = 0.028。
The reactions benzothiophene and 1-bromobenzothiophene with Os-3(CO)(10)(NCMe)(2) have been investigated. The reaction of benzothiophene with Os-3(CO)(10)(NCMe)(2) at 25 degrees C yielded two pro ducts Os-3(CO)(10)(mu-SCCHC6H5)(mu-H), 1 (10%), and Os-3(CO)(9)(mu(3)-SCCC6H5)(mu-H)(2), 2 (8%). Both products were characterized by single crystal X-ray diffraction analyses. Both products contain benzothiophene ligands transformed by the activation of one and two of the C-H bonds, respectively, of the benzothiophene molecule. Compound 1 consists of a closed triosmium cluster with a mu(3)-eta(2)-benzothienyl ligand coordinated to an edge of the cluster through the C-C double bond in the five-membered ring of the ligand. Compound 2 contains a mu(3)-eta(2)-benzothiophyne ligand coordinated to the face of a closed triosmium cluster. Compound 1 was transformed to 2 in 80% yield by heating to 125 degrees C in octane solvent. The reaction of 1-bromobenzothiophene with Os-3(CO)(10)(NCMe)(2) at 25 degrees C yielded two products: Os-3(CO)(10)(mu-SCCHC6H5)(mu-Br), 3 (32%), and Os-3(CO)(9)(mu(3)-SCCHC6H5)(mu-Br), 4 (10%) Both products were characterized by single crystal X-ray diffraction analyses. Both products contain benzothienyl ligands formed by the oxidative addition of the C-Br bond of the bromobenzothiophene to the cluster. In 3 the benzothienyl ligand is coordinated across the open edge of an open triosmium cluster through the sulfur and adjacent carbon atom. In 4 the benzothienyl ligand is a triply bridging ligand using the sulfur atom and the C-C double bond of the five-membered ring. Compound 3 was transformed to 4 in 74% yield by heating to 97 degrees C in heptane solvent for 30 min. Crystal data for 1: space group = P2(1)/n, a = 7.668(2) Angstrom, b = 31.464(5) Angstrom, c = 9.452(2) Angstrom, beta = 105.48(2)degrees, Z = 4, 2563 reflections, R = 0.035. Crystal data for 2: space group = P1 $($) over bar$$, a = 9.791(1) Angstrom, b = 14.576(2) Angstrom, c = 8.094(1) Angstrom, alpha = 95.44(1)degrees, beta = 107.47(1)degrees, gamma = 95.23(1)degrees, Z = 2, 2218 reflections, R = 0.024. Crystal data for 3: space group = P2(1)/c, a = 9.116(2) Angstrom, b = 15.577(3) Angstrom c = 16.270(3) Angstrom, beta = 100.16(1)degrees, Z = 4, 2193 reflections, R = 0.038. Crystal data for 4: space group = P2(1)/n, a = 7.796(1) Angstrom, b = 15.543(3) Angstrom, c = 17.640(2) Angstrom, beta = 90.48(1)degrees, Z = 4, 2288 reflections, R = 0.028.