Pd.H-C Interactions. Preparation and Structure of Orthometalated Tetranuclear Complexes of Palladium(II) and Platinum(II).
Pd.H-C Interactions. Preparation and Structure of Orthometalated Tetranuclear Complexes of Palladium(II) and Platinum(II).
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Pd.H-C 相互作用。
DOI：
10.1021/ic950769q
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发表时间：
1996
影响因子：
4.6
通讯作者：
Y. Kushi
中科院分区：
文献类型：
--
作者：
Tatsuya Kawamoto;I. Nagasawa;H. Kuma;Y. Kushi
2-（1-萘基）苯并噻唑啉与乙酸钯（II）的反应导致螺旋单核和邻位四核产物。用单晶X射线衍射法测定了单核钯[Pd（H1-nabz）（2）]（1）（H（2）1-nabz = 2-N-（1-萘亚甲基氨基）苯硫醇盐）、四核钯[Pd（4）（1-nabz）（4）]（2）和四核铂[Pt（4）（1-nabz）（4）]（3）的分子结构。配合物1的晶体数据如下：a = 14.208（3），B = 18.227（4），c = 14.398（8）; β = 94.55（3）度; V = 3717.0（23）（3）;空间群= P2（1）/n，Z = 4。配合物2的晶体结构参数为：a = B = 15.798（3），c = 23.728（4），V = 5921.7（20）（3），Pd（1-nabz）单元空间群为I ~ 4（1）/a，Z = 16。配合物3的晶体结构为：a = B = 15.496（2），c = 24.348（3），V = 5846.3（20）（3），空间群为I ~ 4（1）/a，Z = 16。单核钯（II）配合物显示邻位氢-钯距离为2.66（7）和2.48（7）π。这些短距离和（1）H NMR研究提供了一个M.H-C相互作用，可以被认为是一个三中心四电子相互作用。2和3的分子结构证实了不寻常的四核化合物的形成，具有罕见的C，N，S-三齿配体来自邻位侧臂orthorbitation的单核钯（II）配合物1的结构和化学性质清楚地表明，1是一个潜在的中间体，在形成的四核配合物2的邻位反应。
The reaction of 2-(1-naphthyl)benzothiazoline with palladium(II) acetate leads to helical mononuclear and orthometalated tetranuclear products. The molecular structures of mononuclear palladium(II) [Pd(H1-nabz)(2)] (1) (H(2)1-nabz = 2-N-(1-naphthylmethylideneamino)benzenethiolate), tetranuclear palladium(II) [Pd(4)(1-nabz)(4)] (2) and tetranuclear platinum(II) [Pt(4)(1-nabz)(4)] (3) have been determined by single-crystal X-ray diffraction method. Crystal data for complex 1 are as follows: a = 14.208(3) Å, b = 18.227(4) Å, c = 14.398(8) Å; beta = 94.55(3) degrees; V = 3717.0(23) Å(3); space group = P2(1)/n, Z = 4. Crystal data for the complex 2 are as follows: a = b = 15.798(3) Å, c = 23.728(4) Å; V = 5921.7(20) Å(3); space group = I4(1)/a, Z = 16 for the Pd(1-nabz) unit. Crystal data for the complex 3 are as follows: a = b = 15.496(2) Å, c = 24.348(3) Å; V = 5846.3(20) Å(3); space group = I4(1)/a, Z = 16 for the Pt(1-nabz) unit. The mononuclear palladium(II) complex reveals short ortho-hydrogen.palladium distances of 2.66(7) and 2.48(7) Å. These short distances and (1)H NMR studies provide a M.H-C interaction which can be regarded as a three-center four-electron interaction. The molecular structures of 2 and 3 confirm the formation of unusual tetranuclear compounds featuring a rare C,N,S-tridentate ligand derived from orthometalation of pendant side arm. The structural and chemical properties of the mononuclear palladium(II) complex 1 clearly suggest that 1 is a potential intermediate in the formation of the tetranuclear complex 2 by orthometalation reactions.