Ni(terpyridine)Cl₂ | 15306-15-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Ni(terpyridine)Cl₂
• 英文别名: Ni(tpy)Cl₂；2,2’;6’,2’’-terpyridine(Ni)Cl₂；tpy(Ni)Cl₂；{Ni(2,2':6',2''-tripyridine)Cl2}；[Ni(2,2':6',2''-terpyridine)Cl2]
• CAS: 15306-15-7
• 化学式: C₁₅H₁₁Cl₂N₃Ni
• 分子量: 362.868
• InChiKey: UEWBEHJJAAWGKE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  Ni(terpyridine)Cl₂ 、 NaSeMes 以 乙醇 、 乙腈 为溶剂， 生成 {Ni(2,2',2''-tripyridine)(2,4,6-trimethylbenzeneselenolate)2}
  参考文献：
  名称：

  Baidya, Narayan; Noll, Bruce C.; Olmstead, Marilyn M., Inorganic Chemistry, 1992, vol. 31, # 14, p. 2999 - 3000

  摘要：

  DOI：
• 作为产物：
  描述：

  α,α,α-三联吡啶 、 nickel(II) chloride hexahydrate 以 乙醇 为溶剂， 以98%的产率得到Ni(terpyridine)Cl₂
  参考文献：
  名称：

  光氧化还原辅助的还原交叉偶联：催化芳基-烷基交叉偶联的机理研究。

  摘要：

  在这里，我们描述了用于两个碳亲电体的直接还原偶联的光氧化还原辅助催化体系。最近的进展表明，镍催化剂对sp 3的偶联具有活性。-碳亲电试剂以及控制良好，光驱动的耦合系统是可能的。我们的系统由镍催化剂，铱光敏剂和胺电子给体组成，能够以高收率偶联卤代烃。光谱学研究支持了一种机理，其中在可见光照射下，Ir光敏剂与三乙醇胺的结合能够还原镍催化剂，并使催化剂朝着碳亲电子试剂的交叉偶联的方向活化。此处开发的合成方法可在1 mol％的催化剂和光敏剂低负荷下运行。催化体系也可以在没有反应添加剂（例如无机盐或碱）的情况下运行。一般有效的sp 2 –sp 3 已经实现了对多种官能团均表现出耐受性的交叉偶联方案。

  DOI：

  10.1021/acs.joc.6b02830

文献信息

• Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions
  作者：Xiaozhou Ma、Elizaveta A. Suturina、Mathieu Rouzières、Mikhail Platunov、Fabrice Wilhelm、Andrei Rogalev、Rodolphe Clérac、Pierre Dechambenoit

  DOI：10.1021/jacs.9b03044

  日期：2019.5.15

  terpyridine; tphz, tetrapyridophenazine) were tailored by changing the oxidation state of the pyrazine-based bridging ligand. While its neutral form mediates a weak antiferromagnetic (AF) coupling between the two S = 1 Ni(II), its reduced form, tphz•-, promotes a remarkably large ferromagnetic exchange of +214(5) K with Ni(II) spins. Reducing twice the bridging ligand affords weak Ni-Ni interactions, in marked

  双核配合物 [(tpy)Ni(tphz)Ni(tpy)] n+（n = 4、3 和 2；tpy，三联吡啶；tphz，四吡啶并吩嗪）中的分子内磁相互作用是通过改变吡嗪的氧化态来调整的——基于桥接配体。虽然它的中性形式介导了两个 S = 1 Ni(II) 之间的弱反铁磁 (AF) 耦合，但其还原形式 tphz•- 促进了 +214(5) K 与 Ni(II) 自旋的非常大的铁磁交换. 减少两倍的桥接配体提供弱的 Ni-Ni 相互作用，与 Co(II) 类似物形成鲜明对比。通过仔细检查所涉及的轨道，这些实验结果提供了对通过芳香桥配体控制磁性交换强度和符号的因素的清晰理解，
• Structural Models of the Bimetallic Subunit at the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase:  Binuclear Sulfur-Bridged Ni−Cu and Ni−Ni Complexes and Their Reactions with CO
  作者：Todd C. Harrop、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ja045284s

  日期：2004.11.1

  bimetallic Mp-Nid site of the A-cluster of acetyl coenzyme A synthase/CO dehydrogenase (ACS/CODH). Reaction of 1 with [Cu(neo)Cl] and [Ni(terpy)Cl2] in MeCN affords the dinuclear complexes (Et4N)[Cu(neo)Ni(NpPepS)] (3) and [Ni(terpy)Ni(NpPepS)] (4), respectively. Reaction of 2 with [Ni(dppe)Cl2] in MeCN yields [Ni(dppe)Ni(PhPepS)] (6). The Ni-Cu complex 3 exhibits no redox chemistry at the Nid site and no reaction

  Ni(II)-二甲酰氨基-二硫醇络合物 (Et4N)2[Ni(NpPepS)] (1) 和 (Et4N)2[Ni(PhPepS)] (2) 用作 Nid 金属合成子，用于构建更高核度的双核 Ni -Cu 和 Ni-Ni 物种模拟乙酰辅酶 A 合酶/CO 脱氢酶 (ACS/CODH) 的 A 簇的双金属 Mp-Nid 位点。1 在 MeCN 中与 [Cu(neo)Cl] 和 [Ni(terpy)Cl2] 反应得到双核配合物 (Et4N)[Cu(neo)Ni(NpPepS)] (3) 和 [Ni(terpy)Ni(NpPepS) )] (4) 分别。2 与 [Ni(dppe)Cl2] 在 MeCN 中的反应生成 [Ni(dppe)Ni(PhPepS)] (6)。Ni-Cu 配合物 3 在 Nid 位点不表现出氧化还原化学反应，也不与 CO 发生反应。相反，4 和 6 中的 Nip 位点很容易被还原（以它们的
• Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase:  Syntheses, Structures, and Reactions with CO
  作者：Todd C. Harrop、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ic0520465

  日期：2006.4.17

  donors have been used to model the bimetallic M(p)-Ni(d) subsite of the A-cluster of the enzyme acetyl coenzyme A synthase/CO dehydrogenase. A series of sulfur-bridged Ni/Cu dinuclear and trinuclear complexes (3-10) have been synthesized to explore their redox properties and affinity of the metal centers toward CO. The structures of (Et4N)2[Ni(PhPepS)] (2), (Et4N)[Cu(neo)Ni(NpPepS)] x 0.5 Et2O x 0.5 H2O

  两种金属合成子，即 (Et4N)2[Ni(NpPepS)] (1) 和 (Et4N)2[Ni(PhPepS)] (2) 包含羧酰胺-N 和硫醇基-S 作为供体已被用于模拟双金属 M( p)-Ni(d) 乙酰辅酶 A 合酶/CO 脱氢酶 A 簇的亚位点。已经合成了一系列硫桥连 Ni/Cu 双核和三核配合物 (3-10) 以探索它们的氧化还原特性和金属中心对 CO 的亲和力。 (Et4N)2[Ni(PhPepS)] (2 ), (Et4N)[Cu(neo)Ni(NpPepS)] x 0.5 Et2O x 0.5 H2O (3 x 0.5 Et2O x 0.5 ), (Et4N)[Cu(neo)Ni(PhPepS)] x (4 x ) ), (Et4N)2[NiNi(NpPepS)}2] x DMF (5 x DMF), (Et4N)2[Ni(DMF)2Ni(NpPepS)}2]
• Anchoring of Metal Complexes on Au₂₅ Nanocluster for Enhanced Photocoupled Electrocatalytic CO₂ Reduction
  作者：Jiangtao Zhao、Abolfazl Ziarati、Arnulf Rosspeintner、Thomas Bürgi

  DOI：10.1002/anie.202316649

  日期：2024.1.2

  Atomically precise Au nanoclusters (NCs) with discrete energy levels can be used as photosensitizers for CO₂ reduction. However, tight ligand capping of Au NCs hinders CO₂ adsorption on its active sites. Here, a new hybrid material is obtained by anchoring of thiol functionalized terpyridine metal complexes (metal=Ru, Ni, Fe, Co) on Au NCs by ligand exchange reactions (LERs). The anchoring of Ru and Ni complexes on Au₂₅ NC (Au₂₅−Ru and Au₂₅−Ni) leads to adequate CO₂ to CO conversion for photocoupled electrocatalytic CO₂ reduction (PECR) in terms of high selectivity, with Faradaic efficiency of CO (FE_CO) exceeding 90 % in a wide potential range, remarkable activity (CO production rate up to two times higher than that for pristine Au₂₅PET₁₈) and extremely large turnover frequencies (TOFs, 63012 h⁻¹ at −0.97 V for Au₂₅−Ru and 69989 h⁻¹ at −1.07 V vs. RHE for Au₂₅−Ni). Moreover, PECR stability test indicates the excellent long‐term stability of the modified NCs in contrast with pristine Au NCs. The present approach offers a novel strategy to enhance PECR activity and selectivity, as well as to improve the stability of Au NCs under light illumination, which paves the way for highly active and stable Au NCs catalysts.

  摘要具有离散能级的原子精密金纳米团簇（NCs）可用作二氧化碳还原的光敏剂。然而，Au NCs 的紧密配体封装阻碍了其活性位点对 CO2 的吸附。在这里，通过配体交换反应（LERs）将硫醇官能化的terpyridine金属配合物（金属=Ru、Ni、Fe、Co）锚定在Au NCs上，获得了一种新的混合材料。在 Au25 NC（Au25-Ru 和 Au25-Ni）上锚定 Ru 和 Ni 复合物后，光耦合电催化二氧化碳还原（PECR）可实现二氧化碳到一氧化碳的充分转化，这体现在以下方面：高选择性，在宽电位范围内一氧化碳的法拉第效率（FECO）超过 90%；显著的活性（一氧化碳产生率比原始 Au25PET18 高出两倍）；以及极高的周转频率（TOFs，63012 h-1 at -0.97 V 时的 TOFs 为 63012 h-1，而 Au25-Ni 在 -1.07 V 时的 TOFs 为 69989 h-1 （相对于 RHE）。此外，PECR 稳定性测试表明，与原始金 NC 相比，改性 NC 具有出色的长期稳定性。本方法为提高 PECR 活性和选择性，以及改善 Au NCs 在光照下的稳定性提供了一种新策略，从而为开发高活性、高稳定性的 Au NCs 催化剂铺平了道路。
• Toward Functional Models of the Nickel Sites in [FeNi] and [FeNiSe] Hydrogenases: Syntheses, Structures, and Reactivities of Nickel(II) Complexes Containing [NiN3S2] and [NiN3Se2] Chromophores
  作者：Christine A. Marganian、Haresh Vazir、Narayan Baidya、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ja00110a013

  日期：1995.2

  The reaction of [Ni(terpy)Cl-2] with similar to 2 equiv of 2,4,6-(Me)(3)C6H2Se- in 3:1 acetonitrile/ethanol affords [Ni(terpy)(2,4,6-(Me)3C(6)H(2)Se)(2)] (7), while [Ni(DAPA)Cl-2] (DAPA = 2,6-bis[1-(phenylimino)ethyl]pyridine) reacts with similar to 2 equiv of PhSe(-) and PhSe(-) in neat ethanol or acetonitrile to yield [Ni(DAPA)(SPh)(2)] (8) and [Ni(DAPA)-(SePh)(2)] (9), respectively. All three complexes contain the distorted trigonal bipyramidal (TBP) NiN(3)E(2) (E = S, Se) chromophore. Previous X-ray absorption spectroscopic data have indicated a distorted TBP NiN3S2 coordination for the nickel site of the hydrogenase (H(2)ase) from Thiocapsa roseopersicina. Complex 7 crystallizes in the monoclinic space group P2(1)/n with a = 13.170(6) Angstrom, b = 16.091(5) A, c = 15.111(8) Angstrom, beta = 114.42(2)degrees, V = 2916(2) Angstrom(3), and Z = 4. The structure of 7 was refined to R = 4.78% on the basis of 2730 reflections (I > 4 sigma(I). Complex 8.CH3-CN crystallizes in the monoclinic space group P2(1)/c with a = 23.012(7) Angstrom, b = 17.814(5) Angstrom, c = 15.698(4) Angstrom, beta = 108.52(2)degrees, V = 6099(5) Angstrom(3), and Z = 8. The structure of 8.CH3CN was refined to R = 6.46% on the basis of 6133 reflections (I > 4 sigma(I)). Complex 9.CH3CN also crystallizes in the monoclinic space group P(2)1/c with a = 23.209(2) Angstrom, b = 17.960(1) Angstrom, c = 15.749(1) Angstrom, beta = 108.482(6)degrees, V = 6225 Angstrom(3) and Z = 8, The structure of 9.CH3CN was refined to 3.90% on the basis of 5808 reflections (I > 4 sigma(I)). Reduction of the terpy analogue 7 with aqueous dithionite gives rise to the corresponding Ni(I) complex which binds CO (reversibly) and H-. The EPR parameters of the CO and hydride adducts resemble the Ni-CO and Ni-C signal of the H(2)ases. Much like the other terpy analogues reported previously by this group, oxidation of 7 affords unstable Ni(III) products in low yields. The two DAPA analogues (8 and 9), on the other hand, are readily oxidized and reduced by biologically relevant oxidants and reductants, and the transformation Ni(III) <-- Ni(II)) --> Ni(I) is reversible. The Ni(III) species (10 and 13) derived from 8 and 9 via oxidation with [Fe(CN)(6)](3-) are comparatively stable and do not bind CO (or H-). The single electron in both 10 and 13 resides in the d(z2) orbital. Upon reduction with aqueous dithionite, 8 and 9 produce the corresponding Ni(I) species 11 and 14 with the single electron in the d(x2-y2) orbital. These Ni(I) complexes are quite stable at low temperatures but slowly lose thiolates/selenolates at room temperature to give [Ni(DAPA)(solv)(2)](+). Both 11 and 14 bind CO reversibly. The affinity of the Ni(I) (but not the Ni(III)) model complexes toward CO strongly suggests the presence of Ni(I) in the C form of the H(2)ases since the enzymes bind CO only in the Ni-C form. Reaction of NaBH4 with 8 and 9 results in the hydride adducts 19 and 20. These hydride adducts are stable under basic conditions. The absence of any detectable proton hyperfine coupling indicates that the H- ligand is located at the basal plane of the Ni(I) center. The EPR parameters of the CO and hydride adducts are quite similar to those of the Ni-CO and Ni-C signals of the H(2)ases.Under basic conditions, both 8 and 9 react with dihydrogen at ambient temperature and pressure to afford the hydride adducts 19 and 20 in significant yields. This reaction is quite remarkable since the model complexes mimic the reductive activation step of the biological nickel site in such a reaction to ultimately produce Ni-C-like signals. Taken together, the present results strongly suggest a Ni(I)-H- formalism for the nickel site in the C form of the H(2)ases. In addition, enhancement of the intensities of the EPR signals of the hydride adducts in the presence of a base indicates heterolytic cleavage of H (coordinated or not) at the Ni(I) site of the model complexes and probably also at the enzyme active sites.