Using London Dispersion Force Effects to Stabilize Inorganic and Organometallic Molecules

利用伦敦色散力效应稳定无机和有机金属分子

• 批准号: 2152760
• 负责人: Philip Power
• 金额: $ 52.5万
• 依托单位: University of California-Davis
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-15 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2152760&HistoricalAwards=false
• 关键词: Using; London; Dispersion; Force; Effects

With the support of the Chemical Synthesis (SYN) Program of the Chemistry Division, Professor Phillip Power, Chemistry Department, University of California–Davis is studying the role of London dispersion (LD) effects in determining the structures and reactivity of inorganic molecules. Chemical bonds often involve the sharing of electrons between two atoms. These are bonds are typically quite strong and are the principal forces that hold many chemical compounds together. However, there are other, usually weaker forces that can influence the behavior of compounds. One of these is called London Dispersion (LD) and results from instantaneously generated electric dipoles that form when non bonded atoms approach one another. While these interactions are weak, they can stabilize normally unstable classes of compounds. The research provides details of how the LD effects can influence molecules leading to structures and reactivity that are counterintuitive. Such interactions have not generally been considered during the preparation of chemicals, but this project seeks to provide the groundwork to utilize LD in the design of new molecules. The project will provide training in sophisticated chemical techniques to a variety of students, including ones from underrepresented groups. In addition, there is an outreach component to K-12 students and teachers that aim to increase the participation of underrepresented groups in science. The main theme of this proposal is the investigation of the effects of the London Dispersion (LD) energies on the structures, stability, and reactivity of sterically crowded inorganic molecules. Despite the weak nature of such interactions (ca. 1 kcal mol-1 /H---H interaction) these are nonetheless ubiquitous and, collectively, can strongly influence molecular properties. Recent LD results have been obtained using terphenyl ligands in which alkyl substituents on two ‘flanking’ aryl rings generate the close H---H approaches for the LD force stabilization. However, in the terphenyl ligands the number of H atoms is limited and they also can interact further via nucleophilic interactions of their flanking rings. To overcome these limitations, ligands that have either less reactive aliphatic rings or rigid hydrocarbon framework groups at the ‘flanking’ positions will be prepared. The ability of these ligands to form and stabilize presently unknown (a) organocopper(I) compounds, (b) compounds with transition metal - main group element bonds, (c) uncomplexed, free-standing dialuminenes and (d) new LDF donor organolithium reagents will be explored. In addition, the use of LD forces in organometallic synthesis, for example, assembling (e) dimetallenes vs. metalylenes and (f) metal-metal bonded complexes in the alkaline earth, and early transition metals will be evaluated. This knowledge is expected to provide useful information on how LD forces enable the assembly of new compound classes.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

加州大学戴维斯分校化学系菲利普鲍尔教授在化学系化学合成项目的支持下，正在研究伦敦色散效应在确定无机分子结构和反应性方面的作用。化学键通常涉及两个原子之间共享电子。这些键通常相当强，是将许多化合物结合在一起的主要力量。然而，还有其他通常较弱的力可以影响化合物的行为。其中之一被称为伦敦色散（LD），是由非键合原子相互接近时瞬间产生的电偶极子引起的。虽然这些相互作用很弱，但它们可以稳定通常不稳定的化合物。该研究提供了LD效应如何影响分子导致违反直觉的结构和反应性的细节。这种相互作用在化学品的制备过程中一般不被考虑，但该项目旨在提供基础，利用LD在新分子的设计。该项目将向各类学生，包括代表性不足群体的学生提供先进化学技术培训。此外，还有一个面向K-12学生和教师的外联部分，旨在增加代表性不足的群体对科学的参与。本论文的主要内容是研究空间拥挤无机分子的伦敦色散（LD）能量对分子结构、稳定性和反应活性的影响。尽管这种相互作用的性质很弱（约。 1 kcal mol-1 /H-H相互作用），但这些都是普遍存在的，总的来说，可以强烈影响分子性质。最近的LD结果已经获得了使用三联苯配体，其中烷基取代基上的两个'侧翼'芳基环产生密切的H-H的方法LD力稳定。然而，在三联苯配体中，H原子的数量是有限的，并且它们还可以通过其侧翼环的亲核相互作用进一步相互作用。为了克服这些限制，将制备在“侧翼”位置具有反应性较低的脂族环或刚性烃骨架基团的配体。将探索这些配体形成和稳定目前未知的（a）有机铜（I）化合物、（B）具有过渡金属-主族元素键的化合物、（c）未络合的、独立的二铝和（d）新的LDF供体有机锂试剂的能力。 此外，将评估LD力在有机金属合成中的使用，例如，组装（e）二金属烯与金属烯和（f）碱土金属和早期过渡金属中的金属-金属键合络合物。该奖项反映了NSF的法定使命，并被认为值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估来支持。

项目成果

London Dispersion Effects on the Stability of Heavy Tetrel Molecules

伦敦色散对重 Tetrel 分子稳定性的影响

• DOI: 10.1002/chem.202301247
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Mears, Kristian L.;Power, Philip P.
• 通讯作者: Power, Philip P.

Sn( ii )–carbon bond reactivity: radical generation and consumption via reactions of a stannylene with alkynes

Sn( ii )–碳键反应性：通过亚锡与炔烃的反应产生自由基和消耗自由基

• DOI: 10.1039/d3cc04014c
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Zou, Wenxing;Mears, Kristian L.;Fettinger, James C.;Power, Philip P.
• 通讯作者: Power, Philip P.

London Dispersion Effects in a Distannene/Tristannane Equilibrium: Energies of their Interconversion and the Suppression of the Monomeric Stannylene Intermediate

远锡烯/三锡烷平衡中的伦敦色散效应：它们相互转化的能量和单体锡烯中间体的抑制

• DOI: 10.1002/anie.202301919
• 发表时间: 2023
• 期刊: Angewandte Chemie International Edition
• 作者: Zou, Wenxing;Bursch, Markus;Mears, Kristian L.;Stennett, Cary R.;Yu, Ping;Fettinger, James C.;Grimme, Stefan;Power, Philip P.
• 通讯作者: Power, Philip P.

A series of ferriostannylenes with differing terphenyl substituents

一系列具有不同三联苯取代基的亚铁亚锡

• DOI: 10.1016/j.jorganchem.2023.122869
• 发表时间: 2023
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Phung, Alice C.;Fettinger, James C.;Power, Philip P.
• 通讯作者: Power, Philip P.

Disproportionation of Sn(II){CH(SiMe 3 ) 2 } 2 to ·Sn(III){CH(SiMe 3 ) 2 } 3 and ·Sn(I){CH(SiMe 3 ) 2 }: Characterization of the Sn(I) Product

Sn(II){CH(SiMe 3 ) 2 } 2 歧化为·Sn(III){CH(SiMe 3 ) 2 } 3 和·Sn(I){CH(SiMe 3 ) 2 }：表征

• DOI: 10.1039/d3cc01542d
• 发表时间: 2023
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Mears, Kristian;Nguyen, Gia-Ann;Ruiz, Bronson;Zou, Wenxing;Fettinger, James C;Power, Philip P
• 通讯作者: Power, Philip P