Synthesis and New Reactivity of Nano-scale Conjugated Transition Metal Molecules

纳米级共轭过渡金属分子的合成及新反应性

基本信息

批准号：
14350476
负责人：
MASHIMA Kazushi
金额：
$ 9.54万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

The construction of one-dimensional, covalently bonded metal strings has attracted much interest in view of fundamental bonding nature as well as promising applications as extensive electronic and optoelectronic materials. Two major synthetic approaches to these compounds have been conducted by (a)using polydentate ligands such as oligo-α-pyridylamido ligands or by (b)partial oxidation of d^8 square-planar complexes to form metal-metal bonds (e.g. platinum blue). Our effort has been focused on aligning transition metals by using a tridentate ligand 6-diphenylphosphino-2-pyridonate (pyphos), in which three different elements, P,N, and O, were linearly laid out by the rigid pyridone framework and could act as coordination sites for arrangement of more than two kinds of transition metals in linear manner. And we have demonstrated linear hetelometallic clusters containing both group VI and group X metals by use of the quadruply-bounded dimolybdenum(II) complex, Mo_2(pyphos)_4 (1)as a core … More part of metal strings such as Mo_2Pd_2Cl_2(pyphos)_4 (2)We have prepared linearly aligned tetranuclear complexes bearing the Rh-Mo-Mo-Rh array and their unique oxidative reaction. We found that rhodium metals at both axial positions of the Mo_2 cluster 1 electronically communicated through the Mo_2 core and, as a result, oxidative reaction Rh(I)/Rh(II) induced the formation of metal-metal bonds.The formation of a metal-nanowire, of which four transition metals are linearly bounded through three metal-metal bonds, was accomplished by oxidation of each Rh(I) atom of 4a by two equiv of (Cp_2Fe)PF_6 to afford [Mo_2Rh_2(Cl)_2(^tBuNC)_4(pyphos)_4](PF_6)_2 (5)accompanied by the formation of two Mo-Rh(II) single bonds and the reduction of bond order of the Mo-Mo moiety.Treatment of Pd_2Cl_2(CNC_6H_3Me_2-2,6)_4 (6)and Mo_2(O_2CCF_3)_4 (7)in dichloromethane afforded an infinite zigzag chain {[Pd_2Cl_2(CNC_6H_3Me_2-2,6)_4][Mo_2(O_2CCF_3)_4]}_n (8), where two metal-metal bonded dinuclear Pd-Pd and Mo-Mo units were bridged by chloro atoms. The Mo-Mo distance (2.1312(3) Å of 8 is significantly elongated compared to that of 7 (2.090(4)) Å) and lies in the range of that of the quadruple Mo-Mo bonded complexes. Such the elongation might be attributed to the axial donation of the chloro atoms of the Pd-Pd unit to the Mo-Mo moiety. Less

一维，共价键合的金属弦的构建引起了人们对基本粘结性质以及承诺的广泛的电子和光电材料的兴趣。通过（a）使用多乙酸配体（例如寡核-α-吡啶基胺配体）或（b）（b）D^8方平面络合物的（b）部分氧化物形成金属金属键（例如Platinum Blathinum Blathum蓝色），对这些化合物进行了两种主要的合成方法。我们的努力一直集中在通过使用三齿配体6-二苯基磷酸2-吡啶酸酯（pyphos）来对齐过渡金属，其中三种不同的元素P，N和O通过僵硬的吡啶酮框架线性地铺设，并且可以用作超过两种换人的局部性的协调位置，以实现多种多样的属性。我们已经证明了通过使用四倍结合的dimolobdenum（ii）复合物，MO_2（pyphos）_4（1）作为核心…作为MO_2PD_2PD_2CL_2（Pyphos）的更多一部分金属条件，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了，我们已经准备好了RH-MO-MO-RH阵列及其独特的氧化反应。我们发现，在MO_2群集1的两个轴向位置的硫辉金属通过MO_2核心进行了电子传播，结果，氧化反应RH（I）/RH（II）诱导了金属金属键的形成。金属纳米的形成。金属纳米的形成。金属纳米的形成，由四个过渡金属通过四个金属构成的oxation（i），iNOM of two y Metal-Metal of（I），Inled（I）成熟（I），Inled（I）成熟（i），Inled（i），Inlede（I），Inled（i）of（i），Inled（I），Inled（I）的氧气键（I），则是INLAIN（I），Inled of（i）的氧化物（I）均为Inal-Metal（I）。 equivalent of (Cp_2Fe)PF_6 to afford [Mo_2Rh_2(Cl)_2(^tBuNC)_4(pyphos)_4](PF_6)_2 (5)accompanied by the formation of two Mo-Rh(II) single bonds and the reduction of bond order of the Mo-Mo moiety.Treatment of PD_2CL_2（CNC_6H_3ME_2-2,6）_4（6）和MO_2（O_2CCF_3）_4（7）在二氯甲烷中提供了无限的曲折链{[[PD_2CL_2（CNC_6H_3ME_2-2,6）_4] [MO_2（O_2CCF_3）_4]} _ N（8），其中两个金属金属键合的二核PD-PD-PD-PD和Mo-Mo单位由Chloro Atoms桥。与7（2.090（4））Å相比，MO-MO距离（2.1312（3）Å的8个距离显着伸长，并且位于四倍体Mo-Mo键合复合物的范围内。这种伸长可能归因于PD-PD单位的氯原子轴向捐赠给Mo-Mo部分。较少的