Cationic gold-antimony complexes: Synthesis and electrophilic properties.
Cationic gold-antimony complexes: Synthesis and electrophilic properties.
批准号:
1856453
负责人:
Francois Gabbai
金额:
$54.25万
依托单位:
依托单位国家:
美国
项目类别:
Continuing Grant
财政年份:
2019
资助国家:
美国
项目状态:
已结题
起止时间:
2019-08-01 至 2023-07-31
中文摘要
催化剂是一种加速或促进化学反应的物质。催化剂对化学和制药行业至关重要,它们被用来减少化学反应所需的能量,并指导精确的化学转化的细节。虽然黄金是一种昂贵的元素,但许多催化剂都包含了它。改进金催化剂是一个重要的研究领域。在这个由化学系化学合成计划资助的项目中,德克萨斯A&M大学化学系的Francois Gabbai教授试图通过将金与非金属元素锑结合来改善金的催化性能。锑能够以一种增强黄金反应性的方式与黄金结合。分离出的金锑化合物被开发成催化烯烃活化的催化剂,而烯烃是主要的化工原料。Gabbai教授参与了面向K-6学生的西班牙语/英语双语课程的外展项目,以吸引年轻学生对科学和技术的兴趣。这项研究项目研究了金(Au)络合物的化学,该络合物的双亲配体由两个膦供体和一个锑部分组成。中心目标是确定锑(Sb)配体的电荷是否可以用来调节金中心的亲电性和催化性能。合成了一系列与五价锑中心紧密相连的金原子的双核配合物,配体抽提反应生成了五价锑中心为单阳离子或阳离子的配合物。结构、光谱和计算研究表明,锑配体上正性的积累是否促进了施主-受主Au-Sb的相互作用。通过烯烃在聚合和氢胺化反应中的催化活性,表明了锑配体的电荷与金中心的亲电活性之间的相关性。这一奖项反映了NSF的法定使命,并通过使用基金会的智力优势和更广泛的影响审查标准进行评估,被认为值得支持。
英文摘要
A catalyst is a substance that speeds or otherwise facilitates a chemical reaction. Catalysts are critical to the chemical and pharmaceutical industries, where they are used to reduce the energy required for chemical reactions and to guide the details of precise chemical transformations. While gold is an expensive element, many catalysts incorporate it. Improving gold catalysts is an important area of investigation. In this project, funded by the Chemical Synthesis Program of the Chemistry Division, Professor Francois Gabbai of the Department of Chemistry at Texas A&M University seeks to improve the catalytic properties of gold by combining it with antimony, a non-metallic element. The antimony is able to combine with gold in a way that enhances gold's reactivity. The gold-antimony compounds that are isolated are developed into catalysts for the activation of alkenes, which are major chemical industry feedstocks. Professor Gabbai participates in outreach programs to K-6 students in Spanish/English dual language programs in order to interest young students in science and technology.This research project investigates the chemistry of gold (Au) complexes featuring ambiphilic ligands comprised of two phosphine donors and an antimony moiety. The central objective is to determine if the charge of the antimony (Sb) ligand can be used to modulate the electrophilic character and catalytic properties of the gold center. A series of dinuclear complexes with a gold atom held in close proximity to a pentavalent antimony center are synthesized and ligand abstraction reactions generate complexes in which the pentavalent antimony center is either monocationic or dicationic. Structural, spectroscopic and computational studies indicate if the accumulation of positive character on the antimony ligand promotes a donor-acceptor Au-Sb interaction. A correlation between the charge of the antimony ligand and the electrophilic reactivity of the gold center is indicated by the catalytic activation of alkenes in polymerization and hydroamination reactions.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.
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Metal→Carbon Dative Bonding
金属—碳配位键
DOI:
10.1002/anie.202201841
发表时间:
2022
期刊:
Angewandte Chemie International Edition
影响因子:
--
作者:
[Litle, Elishua D., Gabbaï, François P.]
通讯作者:
Gabbaï, François P.
Stabilized Carbenium Ions as Latent, Z‐type Ligands
稳定的碳正离子作为潜在的 Z 型配体
DOI:
10.1002/anie.201911662
发表时间:
2019
期刊:
Angewandte Chemie International Edition
影响因子:
--
作者:
[Wilkins, Lewis C., Kim, Youngmin, Litle, Elishua D., Gabbaï, François P.]
通讯作者:
Gabbaï, François P.
DOI:
10.1021/acs.organomet.0c00193
发表时间:
2020-04
期刊:
Organometallics
影响因子:
2.8
作者:
[D. You;Jesse E. Smith;S. Sen;F. Gabbaï]
通讯作者:
D. You;Jesse E. Smith;S. Sen;F. Gabbaï
DOI:
10.1021/acs.organomet.1c00371
发表时间:
2021
期刊:
Organometallics
影响因子:
2.8
作者:
[Smith, Jesse E., Yang, Haifeng, Gabbaï, François P.]
通讯作者:
Gabbaï, François P.
Distiboranes based on ortho -phenylene backbones as bidentate Lewis acids for fluoride anion chelation
基于邻亚苯基主链的二硼烷作为二齿路易斯酸用于氟阴离子螯合
DOI:
10.1039/d1ob00536g
发表时间:
2021
期刊:
Organic & Biomolecular Chemistry
影响因子:
3.2
作者:
[You, Di, Zhou, Benyu, Hirai, Masato, Gabbaï, François P.]
通讯作者:
Gabbaï, François P.
共 12 条
Synthesis, Reactivity, and Photochemistry of Late Transition Metal Complexes Featuring Carbenium-based Ambiphilic Ligands
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批准号:2154972
-
项目类别:Standard Grant
-
资助金额:$55.0万
-
财政年份:2022
-
负责人:Francois Gabbai
-
依托单位:
Design, synthesis, and evaluation of antimony-based anion transporters
-
批准号:2108728
-
项目类别:Standard Grant
-
资助金额:$45.0万
-
财政年份:2021
-
负责人:Francois Gabbai
-
依托单位:
Gold complexes containing redox-active ambiphilic P/Sb ligands: Synthesis, structure and catalytic properties
-
批准号:1566474
-
项目类别:Continuing Grant
-
资助金额:$48.26万
-
财政年份:2016
-
负责人:Francois Gabbai
-
依托单位:
Lewis acidic behavior of organoantimony compounds
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批准号:1300371
-
项目类别:Standard Grant
-
资助金额:$43.97万
-
财政年份:2013
-
负责人:Francois Gabbai
-
依托单位:
Cationic Lewis acids as anion receptors
-
批准号:0952912
-
项目类别:Continuing Grant
-
资助金额:$42.87万
-
财政年份:2010
-
负责人:Francois Gabbai
-
依托单位:
Cationic boranes - Synthesis, reduction, and generation of radicals
-
批准号:0646916
-
项目类别:Continuing Grant
-
资助金额:$39.9万
-
财政年份:2007
-
负责人:Francois Gabbai
-
依托单位:
CAREER: Polydentate Lewis Acids for Anion Recognition and Organic Reaction Catalysis/Establishment of an International Exchange Program for Chemistry Students/Texas A&M Univer
-
批准号:0094264
-
项目类别:Continuing Grant
-
资助金额:$45.3万
-
财政年份:2001
-
负责人:Francois Gabbai
-
依托单位:
国内基金
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基于密度泛函理论金原子簇放射性药物设计、制备及其在肺癌诊疗中的应用研究
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项目类别:面上项目
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基于理论模式GOLD天底数据同化研究热层大气可预报性
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负责人:何建辉
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依托单位:
“合金标准”下测量误差校正模型及其在体育运动数据中的应用
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批准号:10801133
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资助金额:17.0万元
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批准年份:2008
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负责人:张三国
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