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Gyroscope-Like Metal Complexes

类陀螺仪金属配合物

基本信息

批准号：
1566601
负责人：
John Gladysz
金额：
$ 42万
依托单位：
Texas A&M University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2016
资助国家：
美国
起止时间：
2016-07-15 至 2019-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1566601&HistoricalAwards=false
关键词：
Gyroscope Like Metal Complexes

项目摘要

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Gladysz. Professor Gladysz is a faculty member in the Department of Chemistry at Texas A&M University and is developing novel gyroscope-like metal complexes. Macroscopic gyroscopes serve as devices for sensing and/or maintaining the orientation of an object (e.g., space stations; torpedo warheads; virtual reality headsets; mobile phone displays; drones; flying insects via biological assemblies termed "halteres"). The classic mechanical gyroscope, encountered by many as a childhood toy, consists of an axle, a flywheel that can rotate, and a protective housing. When the object is displaced from its axis of rotation, there is a restoring force arising from the conservation of angular momentum. The underlying physics holds at the molecular level, allowing chemists to pursue the limit of gyroscope miniaturization. This project is directed at the synthesis of molecular gyroscopes that contain a metal based flywheel contained in a novel cage-like structure anchored by two phosphorus atoms that are 180° apart. The ease of rotation of the flywheel is maximized, and the demonstration of gyroscopic properties sought. These systems are linked to give "gearboxes", and investigated as catalysts for fine and commodity chemical syntheses, for which metals are commonly required. Since the metals are confined to a restricted space, it is hoped that new selectivities based upon reactant or product size or shape can be realized. This project focuses on the synthesis, fundamental structural and dynamic properties, reactivity, and applications (molecular devices, catalysis) of gyroscope-like metal based molecular rotors. These most commonly feature a trans-diphosphine ligand in which the phosphorus atoms are spanned by three chains, usually of the formula (CH2)n (n 10) but also incorporating hetero-atoms, p-phenylene groups, or other functionalities. They are accessed by three-fold intramolecu-lar ring closing metatheses of precursors of the type trans-LyM(P((CH2)mCH=CH2)3)2, followed by C=C hydrogenation (n = 2m+2). The coordination geometry may be square planar, trigonal bipyramidal, or octahedral (y = 2-4). If the ligands (Ly) are sufficiently small relative the (CH2)n linkages, the LyM unit may rotate within the gyroscope cage. Arrays of gyroscope like units with parallel axes are synthesized with spacings that allow the rotators to interact, enforcing correlated motion such as in gearboxes or waterwheels. The metal fragments are extruded from the gyroscope cages, providing a heretofore unknown class of macrocyclic dibridgehead diphosphines. These are independently synthesized, combined with various metal species to form new gyroscope-like complexes, and (in view of their ability to turn themselves "inside out") investigated as "transport containers" for toxic or harmful metal species.

化学系的化学合成计划支持Gladysz教授的项目。 Gladysz教授是德克萨斯A M大学化学系的一名教员，正在开发新型陀螺仪样金属络合物。宏观陀螺仪用作用于感测和/或保持物体的取向的装置（例如，空间站;鱼雷弹头;虚拟现实耳机;移动的电话显示屏;无人驾驶飞机;通过称为“halteres”的生物组件的飞行昆虫）。经典的机械陀螺仪，许多人遇到的童年玩具，包括一个轴，一个飞轮，可以旋转，和一个保护外壳。当物体偏离其旋转轴时，由于角动量守恒，就有一个恢复力。基本的物理学在分子水平上成立，使化学家能够追求陀螺仪小型化的极限。该项目旨在合成分子陀螺仪，该陀螺仪包含一个金属飞轮，该飞轮包含在一个由两个相隔180°的磷原子锚定的新型笼状结构中。最大限度地提高了飞轮的旋转容易度，并寻求陀螺性能的演示。这些系统被连接到“齿轮箱”，并作为精细和商品化学合成的催化剂进行研究，其中通常需要金属。由于金属被限制在有限的空间内，因此希望可以实现基于反应物或产物尺寸或形状的新的选择性。该项目的重点是合成，基本结构和动力学特性，反应性，和应用（分子器件，催化）的陀螺仪样金属基分子转子。这些最常见的特征是反式二膦配体，其中磷原子被三个链跨越，通常具有式（CH 2）n（n 10），但也包含杂原子、对亚苯基或其他官能团。它们通过trans-LyM（P（（CH 2）mCH= CH 2）3）2类型的前体的三重分子内闭环复分解，然后通过C=C氢化（n = 2 m +2）来获得。配位几何形状可以是正方形平面、三角双锥或八面体（y = 2-4）。如果配体（Ly）相对于（CH 2）n键足够小，则LyM单元可以在陀螺仪笼内旋转。具有平行轴的类似陀螺仪的单元阵列与允许旋转器相互作用的间距合成，从而执行相关运动，例如在齿轮箱或水轮中。金属碎片从陀螺仪笼中挤出，提供了迄今为止未知的一类大环双桥头双膦。这些都是独立合成的，与各种金属物质结合形成新的陀螺仪样络合物，并（鉴于它们能够将自己“从内到外”）作为有毒或有害金属物质的“运输容器”进行研究。

项目成果

期刊论文数量（20）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Partially Shielded Fe(CO) 3 Rotors: Syntheses, Structures, and Dynamic Properties of Complexes with Doubly trans Spanning Diphosphines, trans -Fe(CO) 3 (PhP((CH 2 ) n ) 2 PPh)

部分屏蔽 Fe(CO) 3 转子：双反式二膦配合物的合成、结构和动态性质，反式 Fe(CO) 3 (PhP((CH 2 ) n ) 2 PPh)

DOI：
10.1021/acs.organomet.7b00330
发表时间：
2017
期刊：
Organometallics
影响因子：
2.8
作者：
Steigleder, Esther;Shima, Takanori;Lang, Georgette M.;Ehnbom, Andreas;Hampel, Frank;Gladysz, John A.
通讯作者：
Gladysz, John A.

A Quest for Atropisomerism in Cojoined Square-Planar Metal Complexes: Synthesis and Structures of Sterically Congested Diplatinum Ethynediyl Adducts: A Quest for Atropisomerism in Cojoined Square-Planar Metal Complexes: Synthesis and Structures of Sterica

共联方形平面金属配合物中阻转异构性的探索：空间拥挤二铂乙炔二基加合物的合成和结构：共联方形平面金属配合物中阻转异构性的探索：空间的合成和结构

DOI：
10.1002/ejic.201601307
发表时间：
2017
期刊：
European Journal of Inorganic Chemistry
影响因子：
2.3
作者：
Zhang, Tianyi;Bhuvanesh, Nattamai;Gladysz, John A.
通讯作者：
Gladysz, John A.

Wire like diplatinum, triplatinum, and tetraplatinum complexes featuring X[PtCCCCCCCC] m PtX segments; iterative syntheses and functionalization for measurements of single molecule properties

线状二铂、三铂和四铂络合物，具有 X[PtC-CC-CC-CC-C] m PtX 段；

DOI：
10.1039/c9dt00870e
发表时间：
2019
期刊：
Dalton Transactions
影响因子：
4
作者：
Zheng, Qinglin;Schneider, Jakob F.;Amini, Hashem;Hampel, Frank;Gladysz, John A.
通讯作者：
Gladysz, John A.

Trapping of Terminal Platinapolyynes by Copper(I) Catalyzed 3+2 "Click" Cycloadditions with Organoazides; Probes of Labile Intermediates in Syntheses of Complexes with Extended sp Carbon Chains, and Crystallographic Studies

铜(I)催化的有机叠氮化物的3 2“点击”环加成捕获末端铂多炔；

DOI：
发表时间：
2021
期刊：
Chemistry
影响因子：
0
作者：
Amini, Hashem;Weisbach, Nancy;Gauthier, Sebestian;Kuhn, Helene;Bhuvanesh, Nattamai;Hampel, Frank;Reibenspies, Joseph H;Gladysz, John A.
通讯作者：
Gladysz, John A.

Syntheses and structures of square planar diplatinum butadiynediyl complexes with two different monophosphine ligands on each terminus; probing the feasibility of a new type of inorganic atropisomerism

每个末端具有两个不同单膦配体的方形平面二铂丁二炔二基络合物的合成和结构；