Harnessing the Reactivity of Sulfur: From Novel S-Atom Transfer Reagents to Sulfide-Protected Nanoclusters

利用硫的反应性：从新型 S 原子转移试剂到受硫化物保护的纳米团簇

• 批准号: 2055063
• 负责人: Trevor Hayton
• 金额: $ 50万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2055063&HistoricalAwards=false
• 关键词: Harnessing; Reactivity; Sulfur; Novel; Atom

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Trevor Hayton of the University of California-Santa Barbara will explore the chemistry of sulfide-containing metal complexes. Sulfur plays a key role in industry, medicine, and biology. Underpinning much of this chemistry is the reactivity of metal sulfides. In this project, Professor Hayton will develop several new applications of metal sulfides, including nitric oxide delivery, catalytic sulfur-atom transfer for organic synthesis, and quantum computing. This research will provide excellent training to undergraduate and graduate students in the synthesis and characterization of air-sensitive metal complexes, preparing them for careers in academia, industry, and the national laboratory system. In addition, Professor Hayton will develop a student-led virtual seminar series to introduce students to cutting-edge nanoscience. This series will allow undergraduate students, in particular, to network with researchers from other institutions and meet potential employers. With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Trevor Hayton of the University of California Santa Barbara will perform a wide-ranging investigation into metal sulfide reactivity related to a diverse set of topics, including bioinorganic chemistry, organic synthesis, and nanoscience. In particular, his laboratory will explore the reactions metal sulfides with nitric oxide in an effort to understand the NO/H2S “crosstalk” process, a suite of reactions between NO and sulfide/hydrosulfide in biological systems that is thought to play an important role in cell signaling and the immune response. Additionally, they will explore the ability of the monothiopercarbonate fragment (i.e., the SOC(O)O-dianion) to function as a S-atom transfer reagent. This species is predicted to be a thermodynamically more powerful S-atom source than elemental sulfur, yet should feature good kinetic stability. Finally, they will synthesize and isolate a series of nickel sulfide atomically-precise nanoclusters (APNCs) of varying size. This series of clusters is designed to uncover how paramagnetism emerges in transition metal nanoclusters. Open shell APNCs can feature single molecule magnet (SMM) behavior and have been proposed to function as novel spin qubits.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.

在化学系化学合成项目的支持下，加州大学圣巴巴拉分校的特雷弗·海顿教授将探索含硫化物金属络合物的化学。 硫在工业、医学和生物学中起着关键作用。 这种化学反应的基础是金属硫化物的反应性。 在这个项目中，Hayton教授将开发金属硫化物的几个新应用，包括一氧化氮输送，有机合成的催化硫原子转移和量子计算。 这项研究将为本科生和研究生提供空气敏感金属络合物合成和表征方面的优秀培训，为他们在学术界，工业界和国家实验室系统的职业生涯做好准备。 此外，Hayton教授将开发一个由学生主导的虚拟研讨会系列，向学生介绍尖端的纳米科学。 这一系列将使本科生，特别是网络与其他机构的研究人员，并满足潜在的雇主。在化学系化学合成项目的支持下，加州圣巴巴拉大学的特雷弗·海顿教授将对与各种主题相关的金属硫化物反应性进行广泛的调查，包括生物无机化学，有机合成和纳米科学。 特别是，他的实验室将探索金属硫化物与一氧化氮的反应，以了解NO/H2S“串扰”过程，这是生物系统中NO与硫化物/氢硫化物之间的一系列反应，被认为在细胞信号传导和免疫反应中发挥重要作用。 此外，他们将探索一硫代过碳酸盐片段的能力（即，SOC（O）O-二价阴离子）作为S-原子转移试剂。该物种被预测为比元素硫更强大的硫原子源，但应具有良好的动力学稳定性。最后，他们将合成和分离一系列不同尺寸的硫化镍原子精确纳米团簇（APNC）。 这一系列的团簇旨在揭示顺磁性如何出现在过渡金属纳米团簇中。 开放壳层APNC具有单分子磁体（SMM）特性，并被提议用作新型自旋量子比特。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Photolytic or Oxidative Fragmentation of Trityl Diazeniumdiolate (O 2 N 2 CPh 3 – ): Evidence for Both C–N and N–N Bond Cleavage

三苯甲基二氮烯鎓二醇 (O 2 N 2 CPh 3 – ) 的光解或氧化断裂：C–N 和 N–N 键断裂的证据

• DOI: 10.1021/acs.inorgchem.2c01809
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Baeza Cinco, Miguel Á.;Kräh, Sabrina;Guzman, Camilo F.;Wu, Guang;Hayton, Trevor W.
• 通讯作者: Hayton, Trevor W.

NO and N 2 O Release from the Trityl Diazeniumdiolate Complexes [M(O 2 N 2 CPh 3 ) 3 ] − (M = Fe, Co)

三苯甲基二氮烯鎓二醇络合物释放 NO 和 N 2 O [M(O 2 N 2 CPh 3 ) 3 ] — (M = Fe, Co)

• DOI: 10.1021/acs.inorgchem.2c04088
• 发表时间: 2023
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Baeza Cinco, Miguel Á.;Chakraborty, Arunavo;Guzman, Camilo F.;Kräh, Sabrina;Wu, Guang;Hayton, Trevor W.
• 通讯作者: Hayton, Trevor W.