• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

质子还原反应中具有活性的镍配合物中β-二亚氨基和β-二酮亚胺配体之间的相互作用

Interplay between β-Diimino and β-Diketiminato Ligands in Nickel Complexes Active in the Proton Reduction Reaction.

作者信息

Jameei Moghaddam Navid, Gil-Sepulcre Marcos, Wang Jia-Wei, Benet-Buchholz Jordi, Gimbert-Suriñach Carolina, Llobet Antoni

机构信息

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avda. Països Catalans 16, 43007Tarragona, Spain.

Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007Tarragona, Spain.

出版信息

Inorg Chem. 2022 Oct 24;61(42):16639-16649. doi: 10.1021/acs.inorgchem.2c02150. Epub 2022 Oct 5.

DOI:10.1021/acs.inorgchem.2c02150
PMID:36196853
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9597662/
Abstract

Two Ni complexes are reported with κ-PN β-diimino (BDI) ligands with the general formula Ni(XBDI), where BDI is -(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for (BF) and X = Ph for (BF). Electrochemical analysis together with UV-vis and NMR spectroscopy in acetonitrile and dimethylformamide (DMF) indicates the conversion of the β-diimino complexes and to the negatively charged β-diketiminato (BDK) analogues () and () via deprotonation in DMF. Moreover, further electrochemical and spectroscopy evidence indicates that the one-electron-reduced derivatives and can also rapidly evolve to the BDK () and (), respectively, via hydrogen gas evolution through a bimolecular homolytic pathway. Finally, both complexes are demonstrated to be active for the proton reduction reaction in DMF at = -1.8 V vs Fc, being the active species the one-electron-reduced derivative and .

摘要

报道了两种含有κ-PN β-二亚胺（BDI）配体的镍配合物，通式为Ni(XBDI)，其中BDI为-(2-(二苯基膦基)乙基)-4-((2-(二苯基膦基)乙基)亚氨基)戊-2-烯-2-胺，X表示亚胺内α-碳位置的取代基，(BF)中X = H，(BF)中X = Ph。在乙腈和二甲基甲酰胺（DMF）中进行的电化学分析以及紫外可见光谱和核磁共振光谱表明，β-二亚胺配合物和通过在DMF中去质子化转化为带负电荷的β-二酮亚胺基（BDK）类似物（）和（）。此外，进一步的电化学和光谱证据表明，单电子还原衍生物和也可以分别通过双分子均裂途径释放氢气，迅速演化为BDK（）和（）。最后，两种配合物在相对于Fc为 = -1.8 V时在DMF中对质子还原反应具有活性，活性物种为单电子还原衍生物和。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/b625bad3b0a5/ic2c02150_0013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/9e7683f11cbb/ic2c02150_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/fbbd2b30347a/ic2c02150_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/290229d59734/ic2c02150_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/ff41eb27da53/ic2c02150_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/1e67fd75019b/ic2c02150_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/bb1b81a61b56/ic2c02150_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/47be5332d8ac/ic2c02150_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/0062af5dd1ff/ic2c02150_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/f72599294a9d/ic2c02150_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/1619c76290a1/ic2c02150_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/aa2acc412885/ic2c02150_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/b625bad3b0a5/ic2c02150_0013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/9e7683f11cbb/ic2c02150_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/fbbd2b30347a/ic2c02150_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/290229d59734/ic2c02150_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/ff41eb27da53/ic2c02150_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/1e67fd75019b/ic2c02150_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/bb1b81a61b56/ic2c02150_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/47be5332d8ac/ic2c02150_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/0062af5dd1ff/ic2c02150_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/f72599294a9d/ic2c02150_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/1619c76290a1/ic2c02150_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/aa2acc412885/ic2c02150_0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c20d/9597662/b625bad3b0a5/ic2c02150_0013.jpg

相似文献

1
Interplay between β-Diimino and β-Diketiminato Ligands in Nickel Complexes Active in the Proton Reduction Reaction.质子还原反应中具有活性的镍配合物中β-二亚氨基和β-二酮亚胺配体之间的相互作用
Inorg Chem. 2022 Oct 24;61(42):16639-16649. doi: 10.1021/acs.inorgchem.2c02150. Epub 2022 Oct 5.
2
Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases.含有带侧基氮碱的环状膦配体的镍（II）配合物与氢的相互作用本质。
Proc Natl Acad Sci U S A. 2007 Apr 24;104(17):6951-6. doi: 10.1073/pnas.0608928104. Epub 2007 Mar 8.
3
Volatile beta-ketoiminato- and beta-diketiminato-based zirconium complexes as potential MOCVD precursors.基于挥发性β-酮亚胺基和β-二酮亚胺基的锆配合物作为潜在的MOCVD前驱体。
Inorg Chem. 2003 Nov 3;42(22):7273-82. doi: 10.1021/ic034328f.
4
Cu(i), Ag(i), Ni(ii), Cr(iii) and Ir(i) complexes with tritopic NCN pincer ligands and catalytic ethylene oligomerization.具有三位NCN钳形配体的铜（I）、银（I）、镍（II）、铬（III）和铱（I）配合物及催化乙烯齐聚反应
Dalton Trans. 2019 Sep 14;48(34):12895-12909. doi: 10.1039/c9dt02400j. Epub 2019 Aug 7.
5
Mononuclear nickel(II) dithiolate complexes with chelating diphosphines: Insight into protonation and electrochemical proton reduction.单核镍（II）二硫代配合物与螯合双膦配体：质子化和电化学质子还原的深入研究。
J Inorg Biochem. 2021 Jun;219:111449. doi: 10.1016/j.jinorgbio.2021.111449. Epub 2021 Mar 27.
6
Fine Tunable, Redox Active Octapalladium Chains Supported by Linear Tetraphosphines, Leading to Dynamically 1D Self-Assembled Coordination Polymers.由线性四膦支撑的可精细调节的、氧化还原活性八钯链，形成动态一维自组装配位聚合物。
Chemistry. 2021 Aug 19;27(47):12078-12103. doi: 10.1002/chem.202101715. Epub 2021 Jul 22.
7
Ni(II)/H(2)O(2) reactivity in bis[(pyridin-2-yl)methyl]amine tridentate ligand system. aromatic hydroxylation reaction by bis(mu-oxo)dinickel(III) complex.双[（吡啶-2-基）甲基]胺三齿配体体系中镍（II）/过氧化氢的反应活性。双（μ-氧）二镍（III）配合物引发的芳香族羟基化反应。
Inorg Chem. 2009 Jun 1;48(11):4997-5004. doi: 10.1021/ic900059m.
8
Evolution of nickel speciation during preparation of Ni-SiO(2) catalysts: effect of the number of chelating ligands in [Ni(en)x(H2O)6-2x]2+ precursor complexes.Ni-SiO₂催化剂制备过程中镍形态的演变：[Ni(en)ₓ(H₂O)₆₋₂ₓ]²⁺前驱体配合物中螯合配体数量的影响
Phys Chem Chem Phys. 2006 Apr 14;8(14):1731-8. doi: 10.1039/b513319j. Epub 2006 Feb 28.
9
Comparative DNA binding abilities and phosphatase-like activities of mono-, di-, and trinuclear Ni(II) complexes: the influence of ligand denticity, metal-metal distance, and coordinating solvent/anion on kinetics studies.单核、双核和三核镍（II）配合物的比较DNA结合能力和类磷酸酶活性：配体齿合度、金属-金属距离以及配位溶剂/阴离子对动力学研究的影响
Inorg Chem. 2014 Oct 6;53(19):10731-42. doi: 10.1021/ic501961d. Epub 2014 Sep 16.
10
Cobalt(III) carbonate and bicarbonate chelate complexes of tripodal tetraamine ligands containing pyridyl donors: the steric basis for the stability of chelated bicarbonate complexes.含吡啶基供体的三脚架四胺配体的碳酸钴（III）和碳酸氢盐螯合物：螯合碳酸氢盐配合物稳定性的空间基础
Inorg Chem. 2005 Jun 13;44(12):4215-25. doi: 10.1021/ic0482537.

引用本文的文献

1
Electrocatalytic Hydrogen Evolution using a Nickel-based Calixpyrrole Complex: Controlling the Secondary Coordination Sphere on an Electrode Surface.使用镍基杯吡咯配合物的电催化析氢：控制电极表面的二级配位层
Chemistry. 2023 Nov 21;29(65):e202301920. doi: 10.1002/chem.202301920. Epub 2023 Oct 13.

本文引用的文献

1
Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals.催化氢原子向烯烃的转移：金属氢化物和自由基的路线图。
Chem Sci. 2020 Sep 29;11(46):12401-12422. doi: 10.1039/d0sc04112b. eCollection 2020 Dec 14.
2
Ligand Protonation Triggers H Release from a Dinickel Dihydride Complex to Give a Doubly "T"-Shaped Dinickel(I) Metallodiradical.配体质子化引发二氢二镍配合物释放氢，生成双“T”形二价镍（I）金属双自由基。
Angew Chem Int Ed Engl. 2021 Jan 25;60(4):1891-1896. doi: 10.1002/anie.202011494. Epub 2020 Nov 24.
3
Low-Symmetry β-Diketimine Aryloxide Rare-Earth Complexes: Flexible, Reactive, and Selective.
低对称β-二酮亚胺芳氧基稀土配合物：灵活、反应性和选择性。
Inorg Chem. 2020 Oct 19;59(20):14827-14837. doi: 10.1021/acs.inorgchem.0c02170. Epub 2020 Sep 28.
4
A Phosphine Functionalized β-Diketimine Ligand for the Synthesis of Manifold Metal Complexes.用于合成多种金属配合物的膦功能化β-二酮亚胺配体
Chemistry. 2020 Oct 15;26(58):13191-13202. doi: 10.1002/chem.202001357. Epub 2020 Aug 31.
5
H Evolution from a Thiolate-Bound Ni(III) Hydride.硫醇配体稳定的 Ni(III)氢化物的 H 迁移反应。
J Am Chem Soc. 2020 Apr 29;142(17):7827-7835. doi: 10.1021/jacs.0c00712. Epub 2020 Apr 17.
6
Competing H versus Intramolecular C-H Activation at a Dinuclear Nickel Complex via Metal-Metal Cooperative Oxidative Addition.通过金属-金属协同氧化加成在双核镍配合物上的竞争性氢与分子内碳-氢键活化
J Am Chem Soc. 2020 Apr 8;142(14):6717-6728. doi: 10.1021/jacs.0c00758. Epub 2020 Mar 26.
7
On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation.论分解、降解及伏安偏差：电化学家识别预催化剂转变的现场指南
Chem Soc Rev. 2019 Jun 4;48(11):2927-2945. doi: 10.1039/c8cs00851e.
8
Scandium complexes containing β-diketiminato ligands with pendant phosphanyl groups: competition between Sc/γ-C [4 + 2] cycloaddition and Sc/P frustrated Lewis pair reactions.含有带有侧基膦基的β-二酮亚胺配体的钪配合物：钪/γ-C [4 + 2]环加成与钪/磷受阻路易斯对反应之间的竞争
Dalton Trans. 2019 Jun 14;48(22):7743-7754. doi: 10.1039/c9dt01035a. Epub 2019 May 8.
9
Reduction of CO by a masked two-coordinate cobalt(i) complex and characterization of a proposed oxodicobalt(ii) intermediate.通过一种掩蔽的二配位钴（I）配合物还原一氧化碳以及对一种推测的氧代钴（II）中间体的表征。
Chem Sci. 2018 Nov 9;10(3):918-929. doi: 10.1039/c8sc02599a. eCollection 2019 Jan 21.
10
A β-diketiminate manganese catalyst for alkene hydrosilylation: substrate scope, silicone preparation, and mechanistic insight.用于烯烃硅氢化反应的β-二酮亚胺锰催化剂：底物范围、硅氧烷制备及机理洞察
Chem Sci. 2018 Aug 15;9(39):7673-7680. doi: 10.1039/c8sc02768d. eCollection 2018 Oct 21.