A mixed-valence, hexadecamolybdenum cluster with an Mo-VI cubane 'Jewel' in a 'Setting' of five molybdate(VI)-linked dinuclear Mo-V units

Hill LMR; Abrahams BF; Young CG

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A mixed-valence, hexadecamolybdenum cluster with an Mo-VI cubane 'Jewel' in a 'Setting' of five molybdate(VI)-linked dinuclear Mo-V units

机译：带有六个钼（VI）连接的双核Mo-V单元的“设置”中的带有Mo-VI古巴“珠宝”的混合价十六钼簇

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The hexadecanuclear, mixedvalence cluster [Mo16O42(OH)(2)(3-iPrC(3)H(3)N(2))center dot nH(2)O (1), has been synthesized and characterized by X-ray crystallography, IR spectroscopy and mass spectrometry. The C-2-symmetric complex consists of a cubane (Mo4O4)-O-VI "jewel" held in a 10-point "setting" comprised of five dinuclear Mo-V units tethered together by two tetrahedral Mo-VI centers. The dinuclear units are ligated by twelve 3-isopropylpyrazole units that interact with the Mo-O framework through a network of hydrogen bonds. Structural parameters, charge requirements, and bond valence sum analyses support the assignment of +5 and +6 oxidation states to the dinuclear and cubane/tetrahedral Mo centers, respectively. Space filling models reveal that the pyrazole groups coat much of the surface of the molecule, apart from a number of oxo-rich seams that trace a chiral pattern across the surface. Complex 1 exhibits a unique structure that combines moieties generally atypical of polyoxometalates, viz., a Mo cubane containing only two terminal oxo ligands, and three distinct Mo-2(V) units (including a 5-coordinate Mo center) tethered into a 10-point "setting" by tetrahedral Mo-VI centers.

机译：六癸核混合价簇[Mo16O42（OH）（2）（3-iPrC（3）H（3）N（2））中心点nH（2）O（1）已合成并通过X射线晶体学表征，红外光谱和质谱。 C-2-对称复合物由一个古巴（Mo4O4）-O-VI“珠宝”组成，该珠宝在10点“设置”中包含五个由两个四面体Mo-VI中心束缚的双核Mo-V单元。双核单元与十二个3-异丙基吡唑单元连接，该单元通过氢键网络与Mo-O骨架相互作用。结构参数，电荷要求和键合价和分析支持分别将+5和+6氧化态分配给双核和古巴/四面体Mo中心。空间填充模型显示，吡唑基团覆盖了分子的大部分表面，除了许多在表面上描绘出手性图案的富氧基接缝。配合物1表现出独特的结构，该结构结合了通常是非典型的多金属氧酸盐的部分，即仅包含两个末端氧代配体的Mo古巴和三个拴在一起的Mo-2（V）单元（包括5坐标的Mo中心） Mo-VI四面体的“点”设置。

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《Chemistry: A European journal》 |2008年第9期|共6页
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Hill LMR; Abrahams BF; Young CG;
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正文语种 eng
中图分类化学;
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cluster compounds; molybdenum; polyoxometalates; self-assembly; structure elucidation; BOND-LENGTH RELATIONSHIPS; COORDINATION CHEMISTRY; HYDROTHERMAL SYNTHESIS; OXYGEN; MOLYBDENUM; COMPLEXES; PARAMETERS; OXIDES;

机译：团簇化合物;钼;多金属氧酸盐;自组装;结构阐明;键长关系;配位化学;水热合成;氧;钼;络合物;参数;氧化物;

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1. A mixed-valence, hexadecamolybdenum cluster with an Mo-VI cubane "Jewel" in a "Setting" of five molybdate(VI)-linked dinuclear Mo-V units [J] . Hill LMR, Abrahams BF, Young CG Chemistry: A European journal . 2008,第9期

机译：带有六个钼（VI）连接的双核Mo-V单元的“设置”中的带有Mo-VI古巴“珠宝”的混合价十六钼簇
2. Polymerization of Mo-V: Synthesis and characterization of a dinuclear Mo-V and a hexanuclear mixed-valence Mo-V/Mo-VI complex [J] . Meienberger MD, Morgenstern B, Stucky S, European journal of inorganic chemistry . 2008,第1期

机译：Mo-V的聚合：双核Mo-V和六核混合价Mo-V / Mo-VI配合物的合成与表征
3. A cyclic mixed-valence Mo-VI/Mo-V polyoxothiomolybdate cluster anion stabilized by a [(mu-I){Ag(PPh3)(3)}(2)](+) complex cation. Preparation and structure of [(mu-I){Ag(PPh3)(3)}(2)](2)[Mo8O8(mu-OH)(2)(mu-OEt)(6)(mu-S)(8)(mu(3)-O)(4){Mo(DMF)(2)}] center dot 2EtOH [J] . Wei Wei, Xin Zhifeng, Shi Hua-Tian, Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences . 2015,第8期

机译：[[mu-I] {Ag（PPh3）（3）}（2）]（+）复杂阳离子稳定的环状混合价Mo-VI / Mo-V聚氧硫代钼酸根簇阴离子。 [（mu-I）{Ag（PPh3）（3）}（2）]（2）[Mo8O8（mu-OH）（2）（mu-OEt）（6）（mu-S）（ 8）（mu（3）-O）（4）{Mo（DMF）（2）}]中心点2EtOH
4. Vibronic model of double triangular mixed-valence clusters with spin frustration effects [C] . V. E. Fainzilberg NATO Advanced Research Workshop on Colossal Magnetoresistance and Vibronic Interactions, and the Fifteenth International Symposium on the Jahn-Teller Effect . 2001

机译：旋转挫折效应的双三角混合价簇的振动模型
5. Synthesis, x-ray structure, reactivity, electrochemistry, electronic structure of iron-sulfur cuboidal-type clusters and M-iron-sulfur(z+) cubane-type clusters (M = iron, cobalt, nickel, molybdenum, thallium, copper, silver, zinc and cadmium). [D] . Zhou, Jian. 1996

机译：铁-硫长方体型团簇和M-铁-硫（z +）古巴型团簇（M =铁，钴，镍，钼，th，铜，银）的合成，x射线结构，反应性，电化学，电子结构，锌和镉）。
6. One-Pot Self-Assembly of Dinuclear Tetranuclear and H-Bonding-Directed Polynuclear Cobalt(II) Cobalt(III) and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core [O] . Santokh S. Tandon, Neil Patel, Scott D. Bunge, 2020

机译：二核四核和H键合的多核钴（II）钴（III）和混合价CO（II）/ CO（III）复合物的单核四核和H键合的多核钴（II）具有不完全的双副Cubane核
7. One-Pot Self-Assembly of Dinuclear, Tetranuclear, and H-Bonding-Directed Polynuclear Cobalt(II), Cobalt(III), and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core [O] . Santokh S. Tandon, Neil Patel, Scott D. Bunge, 2020

机译：二核，四核和H键合的多核钴（II），钴（III）和混合价CO（II）/ CO（III）复合物的单核，四核和H键合的多核钴（II），具有不完全的双副Cubane核

A mixed-valence, hexadecamolybdenum cluster with an Mo-VI cubane 'Jewel' in a 'Setting' of five molybdate(VI)-linked dinuclear Mo-V units

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