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

由于一维共价键合金属弦的基本成键性质以及作为广泛的电子和光电材料的广泛应用前景，构建一维共价键合金属弦引起了人们的极大兴趣。这些化合物的两种主要合成方法是：(A)使用多齿配体，如寡聚-α-吡啶酰胺配体；或(B)通过d^8方形平面配合物的部分氧化形成金属-金属键(如铂蓝)。我们的工作集中在使用三齿配体6-二苯基膦-2-吡啶酮(PYPHOS)来排列过渡金属，其中P、N和O三种不同的元素由刚性的吡啶酮骨架线性排列，可以作为两种以上过渡金属以线性方式排列的配位。我们用四键双钼(II)络合物Mo_2(Pyphos)_4(1)作为核心…，证明了含有第VI族和第X族金属的线状杂金属簇合物更多的金属络合物，如Mo_2Pd_2Cl_2(Pphos)_4(2)我们制备了具有Rh-Mo-Mo-Rh阵列的线性排列的四核配合物及其独特的氧化反应。我们发现，在Mo2簇1的两个轴向位置上的Rh金属通过Mo2核以电子方式传递，结果是Rh(I)/Rh(II)氧化反应诱导了金属-金属键的形成。形成了金属-纳米线，其中四种过渡金属通过三个金属-金属键线性结合，Pd_2Cl_2(Cn_2H_3Me_2-2，6)_4(6)和Mo_2(O_2CCF_3)的处理_4(7)在二氯甲烷中形成无限的锯齿链{[Pd_2Cl_2(CNC_6H_3Me_2-2，6)_4][Mo_2(O_2CCF_3)_4]}_n(8)，其中两个金属-金属键合的双核Pd-Pd和Mo-Mo单元由氯原子桥联。与7(2.090(4))Å相比，8的Mo-Mo距离(2.1312(3)Å)显著延长，并且位于四重Mo-Mo键的范围内。这种伸长可能归因于Pd-Pd单元中氯原子对Mo-Mo单元的轴向贡献。较少

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