NaSeMes | 104901-58-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: NaSeMes
• 英文别名: NaSemesityl；sodium 2,4,6-trimethylbenzeneselenolate；sodium;2,4,6-trimethylbenzeneselenolate
• CAS: 104901-58-8
• 化学式: C₉H₁₁Se*Na
• 分子量: 221.136
• InChiKey: VMPFFFXORRLQSW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.59
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  NaSeMes 在 air 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 50.5h， 生成 [Ru(κ²-NMeTs)(2,4,6-trimethylbenzeneselenolate)₂(PPh₃)](OTf)
  参考文献：
  名称：

  4-配位的14电子钌（ii）硫属元素酸盐配合物：合成，电子结构以及与PhICl 2和有机叠氮化物的反应†

  摘要：

  4-配位Ru II硫属元素酸盐复合物[Ru（STipp）2（PPh 3）2 ]（Tipp = 2,4,6-三异丙基苯基，1）和[Ru（SeMes）2（PPh 3）2 ]（Mes = 2合成了（4,6-三甲基苯基，2），并研究了它们与PhICl 2和有机叠氮化物的反应。复杂2从的[Ru合成II（PPH 3）3氯2]和NaSeMes显示一种跷跷板结构，其P–Ru–P和Se–Ru–Se键角分别为103.43（13）和145.26（6）°。自然键序分析表明，在硫族元素孤对和Ru-P反键分子轨道之间，在1和2的每一个中，都有两个n→σ*（供体-受体）π相互作用。两个相互作用的用于计算的第二阶微扰相互作用能量1（20.5和18.3千卡摩尔-1）比那些较强的2（13.6和11.0千卡摩尔-1），表明该配体硫醇盐（TIPPS - ）是一种强π供体比selenolate配体（MESSE -相对于Ru）的II。用PhICl

  DOI：

  10.1039/c9dt02457c
• 作为产物：
  描述：

  双(2,4,6-三甲基苯基)二硒化物 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 NaSeMes
  参考文献：
  名称：

  [PdX2{RE(CH2)nNMe2}] (E = Se, Te; X = Cl, OAc) 配合物的结构变化：实验结果、计算分析和铃木偶联反应中的催化活性

  摘要：

  一系列硫属元素醚配体 RE(CH2)nNMe2 (1) [E = Se 或 Te; R = Ph、o-tol（o-tol = 邻甲苯基）、Mes（Mes = 2,4,6-三甲基苯基）；n = 2 或 3] 及其钯配合物 [PdX2{RE(CH2)nNMe2}]m [X = Cl (2) 或 OAc (3); m = 1, 2] 被合成。配合物 [PdCl2(RECH2CH2NMe2)] [R/E = Ph/Se (2a), Mes/Se (2b), Mes/Te (2c)] 作为单体被分离出来。配合物 [PdCl2(RECH2CH2CH2NMe2)]m [R/E = Ph/Se (2d), Ph/Te (2e), o-tol/Te (2f)] 在溶液中以一种单体和两种二聚体形式存在；它们的比率取决于 NMR 光谱数据显示的 E 和 R。建立了单体 2a、2b、3b、2d、2f 和二聚体 2e

  DOI：

  10.1002/ejic.201402943

文献信息

• Trapping of Payne rearrangement intermediates with arylselenide anions
  作者：Michael E. Jung、Daniel L. Sun

  DOI：10.1016/j.tetlet.2014.11.103

  日期：2015.6

  The intermediate epoxy alcohols prepared via a Payne rearrangement can be trapped with arylselenide anions, giving mixtures of ring-opened products. The 1-arylseleno-2,3-diols are generally favored over the 3-arylseleno-1,2-diols in this process although the reaction of trisubstituted epoxyalcohols, for example, 17, differs from those of disubstituted epoxyalcohols, for example, 21.

  通过Payne重排制备的中间体环氧醇可被芳硒化物阴离子捕获，得到开环产物的混合物。尽管三取代环氧醇（例如17）的反应不同于二取代环氧醇（例如21）的反应，但是在此方法中，1-芳基硒代2,3-二醇通常比3-芳基硒代1,2-二醇更受青睐。。
• Cis configured bis phosphine platinum(II) chalcogenolate complexes: Structures, NMR and computational studies
  作者：Rohit Singh Chauhan、G. Kedarnath、A. Wadawale、D.K. Maity、James A. Golen、Arnold L. Rheingold、Vimal K. Jain

  DOI：10.1016/j.jorganchem.2013.03.030

  日期：2013.8

  Reactions of [PtCl2((PP)-P-boolean AND)] ((PP)-P-boolean AND = dppm, dppe or dppp) with Pb(SMes)(2) and sodium arylchalcogenolates yielded mononuclear complexes of the type, cis-[Pt(EAr) 2(PXP)] [EAr = EMes (E = S, Se or Te; Mes = mesityl), Sepym (pym = 2-pyrimidyl) or SepymMe(2) (pymMe(2) = 4,6-dimethyl-2-pyrimidyl]. These complexes were characterized by elemental analyses and NMR (H-1, P-31) spectroscopy. The molecular structures of [Pt(SeMes)(2)(dppp)]center dot 1\2C(6)H(6), [Pt(TeMes)(2)(dppp)]center dot 3C(6)H(6), [Pt(SeC4H3N2)(2)(dppm)] and [PtSeC4H(4,6-Me2) N2} 2(dppm)]center dot CH2Cl2 were established by single crystal X-ray diffraction analyses. An attempt has been made to rationalize the NMR data with the nature of chelated bis phosphine ligand, chalcogen atom and aryl substituent on the chalcogen atom. The energy difference (Delta E), calculated by DFT, is very small between various conformers. The calculated Delta E between various conformers of mesitylthiolate dppp complex lies in the range of 0.1- 1.0 kcal/ mol; the same for mesitylselenolate complex lies in the range of 0.5e2.2 kcal/ mol and for mesityltellurolate complex it is in the range of 1.0 - 3.0 kcal/ mol. (C) 2013 Elsevier B. V. All rights reserved.
• 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.
• Kersting, Berthold; Krebs, Bernt, Inorganic Chemistry, 1994, vol. 33, # 18, p. 3886 - 3892
  作者：Kersting, Berthold、Krebs, Bernt

  DOI：——

  日期：——
• Synthesis and characterization of the molybdenum(IV) oxo-selenolate complex [MoO(Ph2P(O)CH2CH2P(Ph)CH2CH2PPh2)(Se-2,4,6-(CH3)3C6H2)2]
  作者：P.Michael Boorman、Heinz-Bernhard Kraatz、Masood Parvez

  DOI：10.1016/s0277-5387(00)84974-8

  日期：1993.3

  The presence of adventitious oxygen in the reaction of [(Triphos)MoCl3] (Triphos = Ph2PCH2CH2P(Ph)CH2CH2PPh2) with NaSeC6H2Me3-2,4,6 in THF leads to the formation of [fac-MoO(Ph2P(O)CH2CH2P(Ph)CH2CH2PPh2)(SeC6H2Me3-2,4,6)2]. This is the first example of a structurally characterized molybdenum(IV)oxo-selenolato complex. It contains a chelating triphosphine mono-oxide ligand. The formation can be understood in terms of an oxidative addition of dioxygen to the metal centre followed by oxygen atom transfer to the triphos ligand and reduction of molybdenum to molybdenum(IV).