Synthesis, crystal structure and electrical properties of two new palladium complexes of selenium and sulfur ligands: [NMe4][Pd(C3S3Se2)2]2 and [PMe4][Pd(C3S5)2]2
Synthesis, crystal structure and electrical properties of two new palladium complexes of selenium and sulfur ligands: [NMe4][Pd(C3S3Se2)2]2 and [PMe4][Pd(C3S5)2]2
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两种新型硒硫配体钯配合物的合成、晶体结构和电学性质：[NMe4][Pd(C3S3Se2)2]2和[PMe4][Pd(C3S5)2]2
DOI：
10.1039/dt9940000249
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发表时间：
1994
期刊：
影响因子：
--
通讯作者：
M. Tokumoto
中科院分区：
文献类型：
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作者：
C. Faulmann;J. Legros;P. Cassoux;J. P. Cornelissen;L. Brossard;M. Inokuchi;H. Tajima;M. Tokumoto
化合物[NMe 4][Pd（C3 S3 Se 2）2]2和[PMe 4][Pd（C3 S5）2]2[C3 S3 Se 2 = 4，5-双（氢硒基）-1，3-二硫杂环戊烯-2-磺酸盐; C3 S5 = 4，5-二巯基-1，3-二硫杂环戊烯-2-磺酸酯]是在过量的NMe 4PF 6和PMe 4 I存在下，通过[NBu 4]2[Pd（C3 S3 Se 2）2]和[NBu 4][Pd（C3 S5）2]的电化学氧化制备的，分别用X射线晶体学方法测定了它们的结构。这两种化合物的空间群均为C2/c，与超导相β-[NMe 4][Pd（C3 S5）2]2同构。PdL 2（L = C3 S3 Se 2或C3 S5）实体配对，形成Pd-Pd键长分别为3.174和3.177 A的[（PdL 2）2]二聚体。该结构由在（001）平面中的[（PdL 2）2]二聚体层组成，所述二聚体层通过阳离子片彼此分离。二聚体沿[110]和[10]沿着堆叠。这两种化合物显示出相似的电学性质：室温电导率分别为1.50和1.20 S cm-1;在高温下，电导率与温度的关系很弱，但在低温下突然下降;当施加压力时，电导率增加。在[NMe 4][Pd（C3 S3 Se 2）2]2的反射光谱中观察到宽色散的光激发，表明最高占据（HOMO）和最低未占据分子轨道（LUMO）带以及HOMO型导带的重叠。
The compounds [NMe4][Pd(C3S3Se2)2]2 and [PMe4][Pd(C3S5)2]2[C3S3Se2= 4,5-bis(hydroseleno)-1,3-dithiole-2-thionate; C3S5= 4,5-dimercapto-1,3-dithiole-2-thionate] have been prepared by electrochemical oxidation of [NBu4]2[Pd(C3S3Se2)2] and [NBu4][Pd(C3S5)2] in the presence of a large excess of NMe4PF6 and PMe4I, respectively. Their structures have been determined by X-ray crystallographic methods. Both compounds, with space group C2/c, are isostructural to the superconducting phase β-[NMe4][Pd(C3S5)2]2. The PdL2(L = C3S3Se2 or C3S5) entities are paired, forming [(PdL2)2] dimmers with a Pd–Pd bond length of 3.174 and 3.177 A, respectively. The structure consists of [(PdL2)2] dimer layers in the (001) plane separated from each other by sheets of cations. The dimers are stacked along [110] and [10]. Both compounds show similar electrical properties: the room-temperature conductivities are ≈ 50 and ≈ 20 S cm–1, respectively; at high temperature the conductivity is weakly temperature dependent, but abruptly decreases at low temperatures; the conductivity increases when applying pressure. A broad dispersion of optical excitations was observed in the reflectance spectra of [NMe4][Pd(C3S3Se2)2]2, indicating an overlap of the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) bands and a HOMO-type conduction band.