Complexes in which sp Carbon Chains span two Metals

sp 碳链跨越两种金属的配合物

• 批准号: 0719267
• 负责人: John Gladysz
• 金额: $ 45.8万
• 依托单位: Texas A&M Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-08-01 至 2011-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0719267&HistoricalAwards=false
• 关键词: Complexes; sp; Carbon; Chains; span

The objective of this project is to synthesize complexes in which wire-like sp-hybridized carbon chains span two transition metal fragments, and to conduct detailed studies of their chemical and physical properties. At very long chain lengths, such materials bear a strong conceptual relationship to diamond and graphite, the classical three- and two-dimensional sp3 and sp2-hybridized polymeric carbon allotropes. They are also much more stable than analogs with organic endgroups. Progressively more complex architectures based upon such building blocks will be sought. In one effort, complexes with C32-C40 chains, in which the metal-metal distances would surpass 5 nm, will be targeted; those with C24-C28 chains are easily isolable and stable to 140 C. In another effort, the Cx chain will be sterically protected via two flexible sp3 carbon chains that span donor atoms on each terminus. When sufficiently long, these adopt chiral double helical conformations, much like the insulation about household electrical wire. The redox properties of such species will be studied; it is anticipated that the stabilities of mixed valence radical ions will be enhanced. Other approaches to sterically shielded sp chains involving rotaxanes will be investigated. In another effort, lateral arrays or "bundles" of such complexes with parallel Cx chains will be synthesized. These can be viewed as multi-stranded molecular wires. In another effort, well-defined longitudinally extended arrays, such as PtCxPtCxPtCxPt species, will be prepared. "Alligator clips" will be introduced on the terminal platinum atoms such that single-molecule conductivities can be measured. Reactions with chelating diphosphines may introduce "kinks" that might allow (under appropriate conditions) reductive eliminations to PtC3xPt species or oxidative couplings to polygons that contain platinum atoms at each corner. Polygons will also be prepared by oxidative couplings of monoplatinum species. Attempts will be made to extrude the platinum atoms, generating a cyclocarbon Cx (a monomeric carbon allotrope). Reactions of the C=C moieties will be investigated, such as trimerizations to hexasubstituted benzenes and metatheses to give odd-carbon species M(C=C)n'C=M'. In collaborative efforts, the NLO and photophysical properties of each family of complexes will be characterized. Particular attention will be given to defining chain length effects and chain-chain interactions. A detailed knowledge of how to engineer these wire-like unsaturated molecules into a variety of sophisticated architectures will result.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor John A. Gladysz, of the Department of Chemistry at Texas A&M University. Professor Gladysz and his students are exploring the synthesis and properties of molecules containing extended carbon chains capped by metal atoms. These systems mimic all-carbon systems of considerable current interest. They are expected to display a variety of unusual properties of potential relevance in the design and construction of molecular wires, nonlinear optical materials, and other more complex molecular aggregates. Students involved in this project will have the opportunity to collaborate with students in Germany and with physical chemists specializing in the characterization of molecular materials.

本计画的目标是合成以线状sp杂化碳链跨越两个过渡金属片段的配合物，并对其化学及物理性质进行详细的研究。在非常长的链长，这样的材料承担一个强大的概念关系，金刚石和石墨，经典的三维和二维sp3和sp2杂化聚合碳同素异形体。它们也比具有有机端基的类似物稳定得多。将寻求基于这种构建块的逐渐更复杂的架构。在一项努力中，将靶向具有C32-C40链的络合物，其中金属-金属距离将超过5 nm;具有C24-C28链的那些络合物容易分离并且在140 ℃下稳定。在另一个努力中，Cx链将通过两个柔性sp3碳链进行空间保护，所述柔性sp3碳链跨越每个末端上的供体原子。当足够长时，它们采用手性双螺旋构象，很像家用电线的绝缘体。这些物种的氧化还原性能将进行研究，预计混合价自由基离子的稳定性将得到提高。其他方法空间屏蔽sp链轮烷涉及将进行调查。在另一项努力中，将合成具有平行Cx链的此类复合物的横向阵列或“束”。这些可以被看作是多股分子线。在另一项努力中，将制备良好定义的纵向延伸阵列，例如PtCxPtCxPtCxPt物质。“鳄鱼夹”将被引入终端铂原子，使单分子电导率可以测量。与螯合二膦的反应可能会引入“扭结”，这可能允许（在适当的条件下）还原消除PtC 3xPt物种或氧化偶联到每个角落含有铂原子的多边形。还将通过单铂物质的氧化偶联来制备聚铂酸盐。将尝试挤压铂原子，产生环碳Cx（单体碳同素异形体）。将研究C=C部分的反应，例如三聚成六取代苯和复分解得到奇碳物种M（C=C）n 'C = M'。在合作的努力，非线性光学和每个家庭的配合物的物理性质的特点。将特别注意定义链长效应和链-链相互作用。通过这个奖项，有机和高分子化学计划将支持John A.德克萨斯农工大学化学系的Gladysz说。Gladysz教授和他的学生正在探索含有金属原子覆盖的延伸碳链的分子的合成和性质。这些系统模拟了目前相当感兴趣的全碳系统。它们有望在分子导线、非线性光学材料和其他更复杂的分子聚集体的设计和构建中显示出各种潜在相关的不寻常性质。参与该项目的学生将有机会与德国的学生以及专门从事分子材料表征的物理化学家合作。

项目成果

En route to diplatinum polyynediyl complexes trans,trans-(Ar)(R3P)2Pt(C≡C)nPt(PR3)2(Ar): Untold tales, including end-group strategies

通往二铂聚炔二基配合物 trans,trans-(Ar)(R3P)2Pt(C−C)nPt(PR3)2(Ar) 的途中：不为人知的故事，包括端基策略

• DOI: 10.1351/pac200880030459
• 发表时间: 2008
• 期刊: Pure and Applied Chemistry
• 影响因子: 1.8
• 作者: Stahl, Jürgen;Bohling, James C.;Peters, Thomas B.;de Quadras, Laura;Gladysz, John A.
• 通讯作者: Gladysz, John A.

Syntheses and structural analyses of chiral rhenium containing amines of the formula (η5-C5H5)Re(NO)(PPh3)((CH2)nNRR′) (n=0, 1)

含胺手性铼的合成和结构分析 (η5-C5H5)Re(NO)(PPh3)((CH2)nNRRâ²) (n=0, 1)

• DOI: 10.1016/j.ica.2009.03.047
• 发表时间: 2010
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: Seidel, Sabine N.;Prommesberger, Markus;Eichenseher, Sandra;Meyer, Oliver;Hampel, Frank;Gladysz, John A.
• 通讯作者: Gladysz, John A.

Dreifach-verbrückte Diphosphane mit von innen nach außen invertierender Konfiguration

Dreifach-verbrückte Diphosphane mit von innen nach auàen invertierender 配置

• DOI: 10.1002/ange.201100893
• 发表时间: 2011
• 期刊: Angewandte Chemie
• 作者: Stollenz, Michael;Barbasiewicz, Michał;Nawara-Hultzsch, Agnieszka J.;Fiedler, Tobias;Laddusaw, Ryan M.;Bhuvanesh, Nattamai;Gladysz, John A.
• 通讯作者: Gladysz, John A.

sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(CC)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents

sp 碳链被 sp3 碳双螺旋包围：线状 Pt(CîC)nPt 部分，由两个带有杂原子或烷基取代基的 α,β-二膦跨越

• DOI: 10.1039/b708690n
• 发表时间: 2007
• 期刊: New Journal of Chemistry
• 影响因子: 3.3
• 作者: de Quadras, Laura;Bauer, Eike B.;Stahl, Jürgen;Zhuravlev, Fedor;Hampel, Frank;Gladysz, John A.
• 通讯作者: Gladysz, John A.

Towards multistranded molecular wires: Syntheses, structures, and reactivities of tetraplatinum bis(polyynediyl) complexes with Pt-Cx-Pt-(P(CH2)3P)2-Pt-Cx-Pt-(P(CH2)3P)2 cores (x = 4, 6, 8)

走向多链分子线：四铂双（聚炔二基）配合物的合成、结构和反应活性 - Pt-Cx-Pt-(P(CH2)3P)2-Pt-Cx-Pt-(P(CH2)3P)

• DOI: 10.1039/c002041a
• 发表时间: 2010
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Owen, Gareth R.;Gauthier, Sébastien;Weisbach, Nancy;Hampel, Frank;Bhuvanesh, Nattamai;Gladysz, John A.
• 通讯作者: Gladysz, John A.