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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14350476/
• 关键词: nanoscale; Cluster; Tetranuclear Complexes; Trinuclear complex; Oxidative Reaction; Conjugated system; Addition Reaction; ナノスケール分子; 共役系

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

一维共价键合金属弦的构建由于其基本的成键性质以及作为广泛的电子和光电材料的有前途的应用而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，如低聚-α-吡啶基酰胺配体;或（B）部分氧化d^8正方形平面配合物以形成金属-金属键（如铂蓝）。我们的努力一直集中在通过使用三齿配体6-二苯基膦基-2-吡啶酮（pyphos），其中三个不同的元素，P，N和O，线性地布置在刚性吡啶酮框架，并可以作为两种以上的过渡金属以线性方式排列的配位位点排列的过渡金属。以四配位键合的二钼（II）配合物Mo_2（pyphos）_4（1）为核，我们证明了同时含有第VI族和第X族金属的线性杂原子簇合物 ...更多信息 部分金属串如Mo_2Pd_2Cl_2（pyphos）_4。（2）我们合成了具有Rh-Mo-Mo-Rh阵列的线性排列四核配合物及其独特的氧化反应。发现Mo_2团簇1的两个轴向位置上的铑金属通过Mo_2核进行电子交换，并通过氧化反应Rh（I）/Rh（II）诱导金属-金属键的形成，从而形成由四种过渡金属通过三种金属-金属键线性键合的金属-纳米线，通过2当量的（Cp_2Fe）PF_6氧化4a中的每个Rh（I）原子得到[Mo_2Rh_2（Cl）_2（^tBuNC）_4（pyphos）_4]（PF_6）_2（5），同时形成两个Mo-Rh（II）Pd_2Cl_2的处理（CNC_6H_3Me_2- 2，6）_4（6）和Mo_2（O_2CCF_3）_4（7）在二氯甲烷中反应得到无限锯齿形链{[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单元通过氯原子桥接。Mo-Mo键距（2.1312（3））与7（2.090（4））相比明显变长，并处于四重Mo-Mo键合配合物的范围内。这种伸长可能归因于Pd-Pd单元的氯原子向Mo-Mo部分的轴向捐赠。少

项目成果

H.Tsurugi: "Unusual Enhancement of Ethylene Polymerization Activity of Benzyl Zirconium Complexes by Benzylation of the IminoMoiety"Chemistry Letters. 32・8. 756-757 (2003)

H.Tsurugi：“亚氨基部分的苄基化对苄基锆配合物的乙烯聚合活性的异常增强”，《化学快报》32・8（2003）。

Y.Matsuo: "Synthesis and Structural Characterization of 2,5-Bis(N-aryliminomethyl)pyrrolyl Complexes of Aluminum"Bull.Chem.Soc.Jpn.. 76. 1965-1968 (2003)

Y.Matsuo：“2,5-双(N-芳基亚氨基甲基)吡咯基铝配合物的合成和结构表征”Bull.Chem.Soc.Jpn.. 76. 1965-1968 (2003)

Unique Oxidative Metal-Metal Bond Formation of Linearly Aligned Tetranuclear Rh-Mo-Mo-Rh Clusters

线性排列四核 Rh-Mo-Mo-Rh 团簇的独特氧化金属-金属键形成

• 发表时间: 2004
• 期刊: J.Am.Chem.Soc. 126
• 作者: T.Rueffer

K.Mashima: "Unique ring-methyl Deprotonation of μ^4-1,2-dimethyl-3,4-di(tert-butyl)cyclobutadiene Complexes of Palladium(II) Bearing Phosphine Ligand"Inorg.Chim.Acta. 352. 105-109 (2003)

K.Mashima：“带有膦配体的钯 (II) 配体的 μ^4-1,2-二甲基-3,4-二（叔丁基）环丁二烯配合物的独特环甲基去质子化”Inorg.Chim.Acta 352。 105-109（2003）

Construction of Metal-Centered Chirality : Diastereoselective Addition of the Meerwein Reagent (Me_3OBF_4) to Rhodium Carbonyl Complexes Having the Cp'-P Ligand

金属中心手性的构建：Meerwein 试剂 (Me_3OBF_4) 与具有 Cp-P 配体的羰基铑配合物的非对映选择性加成

• 发表时间: 2004
• 期刊: Organometallicsc 23(9)
• 作者: Kataoka;Yasutaka;Nakagawa;Yousuke;Shibahara;Atsushi;Yamagata;Tsuneaki;Mashima;Kazushi;Tani;Kazuhide
• 通讯作者: Kazuhide