[platinum(II)(bipyridine)(1,2-benzenedithiiolate)] | 198770-15-9

• 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: [platinum(II)(bipyridine)(1,2-benzenedithiiolate)]
• 英文别名: [platinum(II)(bipy)(1,2-benzenedithiiolate)]；[Pt(o-bdt)(bpy)]；[Pt(o-benzenedithiolate)(bpy)]；[(bpy)Pt(1,2-benezenedithiolate)]；(2,2'-bipyridine)(1,2-benzenedithiolate)platinum(II)；2,2'-bipyridine(1,2-benzenedithiolato)platinum(II)；(Pt(2,2'-bipyridine)(1,2-benzenedithiolato))；[(bipyridine)Pt(1,2-benezenedithiolate)]；(Pt(bpy)(bdt))；[(2,2'-bipyridine)Pt(1,2-benzenedithiol-2H)]；[Pt(1,2-benzenedithiolate)(2,2'-bipyridine)]；Pt(2,2'-bipyridine)(1,2-benzenedithiolate)；[(bpy)Pt(bdt)]；[Pt(dbt)(bpy)]；Benzene-1,2-dithiolate;platinum(2+);2-pyridin-2-ylpyridine
• CAS: 198770-15-9
• 化学式: C₁₆H₁₂N₂PtS₂
• 分子量: 491.497
• InChiKey: ZHIGTFRYQLMTQP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [platinum(II)(bipyridine)(1,2-benzenedithiiolate)] 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  铂 (II) 二亚胺二硫醇盐的光氧化

  摘要：

  Pt(bpy)(bdt)（bpy = 2,2'-联吡啶；bdt = 1,2-苯二硫醇盐）的紫色是由于 Pt/S → 二亚胺电荷转移转变；发射源自相应的三重态 (τ = 460 ns)。Pt(bpy)(bdt)在N,N-二甲基甲酰胺、乙腈或二甲亚砜溶液中存在氧气时发生光化学氧化；该反应已通过 1H NMR 和紫外-可见吸收光谱进行了研究。由激发复合物的能量转移产生的单线态氧被认为是活性氧物种，在亚磺酸盐 Pt(bpy)(bdtO2) 和二亚磺酸盐 Pt(bpy)(bdtO4) 产品的连续形成中。两种产品均已通过 X 射线晶体学表征。光氧化速率强烈依赖于水的浓度，和瞬态吸收光谱与至少一种中间体的形成一致。总的来说，我们的数据表明铂 (II) 二亚胺二硫醇盐的光氧化化学类似于有机...

  DOI：

  10.1021/ja9723803
• 作为产物：
  描述：

  (2,2-联吡啶)二氯铂(II) 、 disodium benzene-1,2-dithiolate 以 二甲基亚砜 为溶剂， 以72%的产率得到[platinum(II)(bipyridine)(1,2-benzenedithiiolate)]
  参考文献：
  名称：

  Photochemical and Chemical Oxidation of α-Dimine−Dithiolene Metal Complexes: Insight into the Role of the Metal Atom

  摘要：

  [Pd(bpy)(bdt)], 2 (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate), was prepared in good yield by the reaction of bdtNa(2) with [(bpy)PdCl2] in DMSO. The analogous nickel complex, 1, was prepared in a similar reaction using MeOH/CH2Cl2 and [(bpy)NiCl2. dmf](2). Both 1 (a = 7.99'10(1) Angstrom, b = 11.4385(1) Angstrom, c = 16.1415(1) Angstrom, beta = 103.327(1)degrees, V = 1435.86(2) Angstrom (3), Z = it) and 2 (a = 8.1631(5) A, b = 11.4379(7) Angstrom, c = 16.2475(10) Angstrom, beta = 103.7010(10)degrees V = 1473.84(12) Angstrom (3), Z = 4) crystallize in the monoclinic space group P2(1)/c and are isostructural with their previously reported platinum analogue. In accord with the results observed for platinum but not nickel, photochemical oxidation of 2 in DMF provides the monosulfinate complex [Pd(bpy)(bdtO(2))], 4, along with a minor amount of the corresponding disulfinate [Pd(bpy)(bdtO(4))], 5, while chemical oxidation yields only the latter. 4 cocrystallizes with 5 in the monoclinic space group P2(1)/c (a = 8.026(3) Angstrom, b = 14.600(6) Angstrom, c = 13.371(3) Angstrom, beta = 101.80(3)degrees, V = 1533.8(9) Angstrom (3), Z = 4) as does pure 5 (a = 8.5611(9) Angstrom, b = 14.4586(15) Angstrom, c = 13.3677(14) Angstrom. beta = 108.122(2)degrees, V = 1572.6(3) Angstrom (3), Z = 4). Comparison of spectroscopic and electrochemical properties of the three complexes, [M(bpy)(bdt)], yields the following ordering for the energy of the HOMO: Pd < Ni < Pt. The observed reactivity patterns and the electronic data suggest that the "anomalous" reactivity of 1 be attributed to the greater relative flexibility of the coordination geometry for nickel(II) complexes rather than electronic differences such as the energies of the frontier orbitals.

  DOI：

  10.1021/ic000884n

文献信息

• Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes
  作者：Bo Zheng、Randy P. Sabatini、Wen-Fu Fu、Min-Sik Eum、William W. Brennessel、Lidong Wang、David W. McCamant、Richard Eisenberg

  DOI：10.1073/pnas.1509310112

  日期：2015.7.28

  The light-driven generation of H ₂ , the reductive side of water splitting, requires a light absorber or photosensitizer (PS) for electron-hole creation and photoinduced electron transfer. To increase the effectiveness of charge transfer chromophores as PSs, this report describes the attachment of a strongly absorbing organic dye (dipyrromethene-BF ₂ , commonly known as Bodipy) to Pt diimine dithiolate charge transfer chromophores and examination of systems containing these dyads for the light-driven generation of H ₂ . The use of these dyads increases system activity under green light irradiation (530 nm) relative to systems with either chromophore alone, validating such an approach in designing artificial photosynthetic systems. One dyad system exhibits both high activity and substantial durability (40,000 turnovers relative to PSs over 12 d).

  标题: 重要性 光驱动的H2生成，即水分裂的还原端，需要光吸收剂或光敏剂（PS）来产生电子-空穴并进行光诱导电子转移。为了增加电荷转移色素作为光敏剂的有效性，本报告描述了将强吸收的有机染料（二吡咯甲烷-BF2，通常称为Bodipy）附着到Pt二亚甲基二硫酸盐电荷转移色素上，并检查包含这些二聚体的系统对光驱动的H2生成的影响。使用这些二聚体在绿光照射（530 nm）下增加了系统活性，相对于仅有色素的系统，验证了这种设计人工光合系统的方法。其中一种二聚体系统表现出高活性和相当的耐久性（相对于PS在12天内的40,000次循环）。
• A Convenient Approach to Luminescent Cyclometalated Platinum(II) Complexes with Organometallic π‐Bonded Benzenedithiolate
  作者：Hugo Sesolis、Geoffrey Gontard、Anny Jutand、Maria Pia Gullo、Elisa Bandini、Andrea Barbieri、Hani Amouri

  DOI：10.1002/ejic.201800561

  日期：2018.9.16

  cyclometalated platinum(II) complexes [(C^N)Pt(η-S^S)] with π-bonded benzenedithiolate (η-S^S) = Cp*Ru(C6H4S2)} and various cyclometalated ligands, (C^N) = 2-phenylpyridine (ppy), (2); 2,4-difluorophenylpyridine (F2ppy) (3), benzo[h]quinoline (bzq) (4); dibenzo[f,h]quinoline (dbzq) (5) } were prepared and fully characterized. For comparison purposes the related bipyridine platinum (II) complex [(bpy)Pt(η-S^S)][OTf]

  一系列中性环金属化铂 (II) 配合物 [(C^N)Pt(η-S^S)] 与 π 键合苯二硫醇 (η-S^S) = Cp*Ru(C6H4S2)} 和各种环金属化配体, (C^N) = 2-苯基吡啶 (ppy), (2); 2,4-二氟苯基吡啶（F2ppy）（3），苯并[h]喹啉（bzq）（4）；二苯并 [f,h] 喹啉 (dbzq) (5) } 已制备并充分表征。为了比较的目的，还制备了相关的联吡啶铂(II)配合物[(bpy)Pt(η-S^S)][OTf](6)。研究了这些配合物的电化学行为，结果表明，由于 Cp*Ru 部分的存在，这些化合物对氧化的稳定性增强，该部分现在与苯二硫醇基 π 键合。此外，通过单晶 X 射线分子结构鉴定了几种配合物。据我们所知，这些是第一个报道的带有 π 键合苯二硫醇 (bdt) 配体的环金属化铂配合物的结构。所有配合物在室温下在流体溶液中和在 77 K 下
• Induced phosphorescence from Pt → Ag and Ag(<scp>i</scp>)⋯Ag(<scp>i</scp>) metallophilic interactions in benzenedithiolatodiimine-Pt₂/Ag₂ clusters: a combined experimental and theoretical investigation
  作者：Jamal Moussa、Lise Marie Chamoreau、Maria Pia Gullo、Alessandra Degli Esposti、Andrea Barbieri、Hani Amouri

  DOI：10.1039/c5dt03702f

  日期：——

  ascertained by a single-crystal X-ray diffraction study and shows that the assembly is identified as [(Pt2Ag2(o-bdt)2(bpy)2](CF3SO3)2 (2). Remarkably, the structure shows that complex 2 exists as two isomers I and II displaying different types of argentophilic interactions Ag⋯Ag as well as Pt → Ag dative bonds. These interactions are highly important and turn on phosphorescent emissions at low temperature

  我们报告了一种新型的铂（II）-银（I）簇的合成和发光性质，该簇表现出超分子供体-受体的Pt→Ag键以及d 10 ⋯d 10亲银性相互作用。通过将三氟甲磺酸银与[Pt（bdt）（bpy）]（1）构件混合，通过自组装方法获得该化合物。通过红外，NMR（1 H，13 C）和UV-可见光谱对新化合物进行表征。此外，通过单晶X射线衍射研究明确确定了分子结构，结果表明该组装体被鉴定为[（Pt 2 Ag 2（o -bdt）2（bpy） 2 ]（CF 3 SO 3） 2（ 2）。值得注意的是，该结构表明配合物2以两个异构体I和II的形式存在，表现出不同类型的亲银相互作用Ag⋯Ag以及Pt→Ag亲和键。这些相互作用非常重要，并根据异构体的性质在低温下开启磷光发射。通过TD-DFT计算研究和合理化了这两种异构体的光物理性质。这项工作为合成新型的超分子组装体铺平了道路，该组装体表现出了亲金属以及供体-受体金属-金属相互作用所赋予的独特性能。
• Sequential Photooxidation of a Pt(II) (Diimine)cysteamine Complex: Intermolecular Oxygen Atom Transfer versus Sulfinate Formation
  作者：Dong Zhang、Ye Bin、Lorillee Tallorin、Florence Tse、Blanca Hernandez、Errol V. Mathias、Timothy Stewart、Robert Bau、Matthias Selke

  DOI：10.1021/ic3020578

  日期：2013.2.18

  The thiolato complex [platinum(II) (bipyridine)(N,S-aminoethanethiolate)](+)Ch(-) (1) undergoes sequential reactions with singlet oxygen to initially form the corresponding sulfenato complex [platinum(II) (bipyridine)(N,S(=O)-aminoethansulfenate)](+) (2) followed by a much slower reaction to the corresponding sulfinato complex. In contrast with many platinum dithiolato complexes, 1 does not produce any singlet oxygen, but its rate constant for singlet oxygen removal (k(T)) is quite large (3.2 x 10(7) M-1 s(-1)) and chemical reaction accounts for ca. 25% of the value of k(T). The behavior of 1 is strikingly different from that of the complex platinum(II) (bipyridine)(1,2-benzenditholate) (4). The latter complex reacts with 102 (either from an external sensitizer or via a self-sensitized pathway) to form a sulfinato complex. These two very different reactivity pathways imply different mechanistic pathways: The reaction of 1 with O-1(2) must involve O-O bond cleavage and intermolecular oxygen atom transfer, while the reactive intermediate in complex 4 collapses intramolecularly to the sulfinato moiety.