hexafluoro-l6-arsane, [5,5'-bi(1,3,2,4-dithiadiazole)]-1,1'-diium salt | 134589-41-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: hexafluoro-l6-arsane, [5,5'-bi(1,3,2,4-dithiadiazole)]-1,1'-diium salt
• CAS: 134589-41-6
• 化学式: 2AsF₆*C₂N₄S₄
• 分子量: 586.137
• InChiKey: LHDZLCNSUPXYRA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.56
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  hexafluoro-l6-arsane, [5,5'-bi(1,3,2,4-dithiadiazole)]-1,1'-diium salt 在 二氧化硫 、 三苯基锑 、 四甲基氯化铵 作用下， 生成
  参考文献：
  名称：

  5,5′-bi(1,3,2,4-dithiadiazolylium)(2+) bis[hexafluoroarsenate(V)]: a general synthetic strategy to molecules and radicals containing thiazyl rings

  摘要：

  The salt [SNS][AsF6] undergoes a quantitative multiple cycloaddition reaction with cyanogen to give the planar, centrosymmetric dication (CNSNS)22+, which has been characterised by vibrational and C-13 NMR spectroscopy, chemical analysis and X-ray crystallography. While the reaction between cyanogen and SNS+ must proceed via a 1 : 1 cycloadduct, NCCNSNS+, this was not prepared or observed. The cycloaddition of SNS + to NCCNSNS+ must therefore be kinetically preferred, contrary to arguments based on simple frontier molecular orbital (FMO) theory. By contrast, the reaction of [SNS][AsF6] with [N=CCNSNSCH][AsF6]to give [HCSNSC-CNSNS][AsF6]2 was complete only after 10 weeks at 50-degrees-C, in complete accord with FMO theory. These results are rationalised in terms of the influence of high-energy, in-plane molecular orbitals and the electrostatic interaction between SNS+ and the slightly negatively charged nitrogen atom (N) in the CNSNS+ ring, which facilitates the second cycloaddition. The salt [(CNSNS)2][AsF6]2 potentially provides access to a new family of eight other bicyclic CNS dications, radical cations and diradicals, of which .SNSNC-CNSNS+, +SNSNC-CNSSN. and +NSSNC-CNSNS+ are reported.

  DOI：

  10.1039/dt9930001499
• 作为产物：
  描述：

  氰 在 六氟偶砷酸(V)二硫杂硝鎓 、 二氧化硫 作用下， 反应 120.0h， 以97%的产率得到hexafluoro-l6-arsane, [5,5'-bi(1,3,2,4-dithiadiazole)]-1,1'-diium salt
  参考文献：
  名称：

  5,5′-bi(1,3,2,4-dithiadiazolylium)(2+) bis[hexafluoroarsenate(V)]: a general synthetic strategy to molecules and radicals containing thiazyl rings

  摘要：

  The salt [SNS][AsF6] undergoes a quantitative multiple cycloaddition reaction with cyanogen to give the planar, centrosymmetric dication (CNSNS)22+, which has been characterised by vibrational and C-13 NMR spectroscopy, chemical analysis and X-ray crystallography. While the reaction between cyanogen and SNS+ must proceed via a 1 : 1 cycloadduct, NCCNSNS+, this was not prepared or observed. The cycloaddition of SNS + to NCCNSNS+ must therefore be kinetically preferred, contrary to arguments based on simple frontier molecular orbital (FMO) theory. By contrast, the reaction of [SNS][AsF6] with [N=CCNSNSCH][AsF6]to give [HCSNSC-CNSNS][AsF6]2 was complete only after 10 weeks at 50-degrees-C, in complete accord with FMO theory. These results are rationalised in terms of the influence of high-energy, in-plane molecular orbitals and the electrostatic interaction between SNS+ and the slightly negatively charged nitrogen atom (N) in the CNSNS+ ring, which facilitates the second cycloaddition. The salt [(CNSNS)2][AsF6]2 potentially provides access to a new family of eight other bicyclic CNS dications, radical cations and diradicals, of which .SNSNC-CNSNS+, +SNSNC-CNSSN. and +NSSNC-CNSNS+ are reported.

  DOI：

  10.1039/dt9930001499

文献信息

• The kinetics of the quantitative, symmetry allowed, reverse electron demand cycloadditions of the pseudo-1,3-dipole SNS⁺with alkynes and nitriles; the preparation and X-ray crystal structures of NCCSNSCHAsF₆and SNSNC–CNSNS(AsF₆)₂: the precursor to a new class of S₂N₂C–CN₂S₂ⁿ⁺(n= 0,1,2) bicyclics
  作者：Simon Parsons、Jack Passmore、Melbourne J. Schriver、Peter S. White

  DOI：10.1039/c39910000369

  日期：——

  The rates of cycloaddition reactions of SNSAsF6 with alkynes and nitriles increase as the ionization potential (Ei) of the triple bond decreases, and accordingly reaction with HCCCN occurs preferentially at the CC bond; however, it reacts with NCCN quantitatively to give the dication ([graphic omitted])22+, from which several members of a new family of S2N2C–CN2S2n+(n= 0,1,2) bicyclics have been prepared.

  SNSAsF6与炔烃和腈的环加成反应速率随着三键电离势（Ei）的降低而增加，因此与HCCCN的反应优先发生在CC键上；然而，它与NCCN定量反应生成二阳离子（[图形省略]）22+，从中制备出了新系列S2N2C–CN2S2n+（n= 0,1,2）双环化合物的若干成员。
• Preparation and Characterization of (CNSSS)₂(A)₂ (A = AsF₆⁻, SbF₆⁻, Sb₂F₁₁⁻) Containing the O₂-like 5,5′-Bis(1,2,3,4-trithiazolium) Dication: The Second Example of a Simple Nonsterically Hindered Main-Group Diradical That Retains Its Paramagnetism in the Solid State
  作者：T. Stanley Cameron、Andreas Decken、Friedrich Grein、Carsten Knapp、Jack Passmore、J. Mikko Rautiainen、Konstantin V. Shuvaev、Robert C. Thompson、Dale J. Wood

  DOI：10.1021/ic100760t

  日期：2010.9.6

  (ΔEST = 2J) of <±2 cm−1. CASPT2[12,12]/6-311G* calculations support a triplet ground state with a small singlet−triplet gap. The single-crystal electron paramagnetic resonance (EPR) of 7(Sb2F11)2 doped in 10(Sb2F11)2 is in agreement with the triplet state arising from the weak coupling between the unpaired electrons residing in pπ orbitals in each of the rings. Variable-temperature susceptibility data

  NC-CN与S 4（MF 6）2和S 8（MF 6）2（M = As，SB）1：1混合物（化学计量上等同于四个“ S 3 MF 6 ”单元）的反应导致S 3 NCCNS 3（MF 6）2 [ 7（MF 6）2 ]的定量形成，它是该反应中的热力学吸收剂。SB的2 ˚F 11 -盐7（SB 2 ˚F 11）2通过加入过量的SBF的制备5至7（ASF 6）2。对所有三种盐的晶体结构测定表明，可以将7 2+视为通过C C单键连接在一起的两个R-CNS 3 +自由基阳离子。由于静电Nδ- ··· Sδ+，两个环共面并且处于反方向互动。根据计算的估计值和π键能量的简单比较，未遵守遵循八位位组规则的经典键合替代方案（五面体结构），并且能量更高。计算出的分子轨道（MOs）支持这一点，表明对应于喹啉结构的MO的能量比几乎简并的7 2+单占据的MO更高。根据法向坐标分析和以PBE0 / 6-31G *水平计算的理论振动频率，确定所有盐中7
• The neutral diradical 5,5<i>'</i>-bis(1,3,2,4-dithiadiazolyl) [-], the first main group radical to exhibit a dramatic increase in paramagnetism on mechanical grinding
  作者：Guillermo Antorrena、Scott Brownridge、T Stanley Cameron、Fernando Palacio、Simon Parsons、Jack Passmore、Laurence K Thompson、Fitri Zarlaida

  DOI：10.1139/v02-149

  日期：2002.11.1

  Reduction of [([Formula: see text])₂][As₆]₂ with triphenylantimony and tetrabutylammonium chloride produced the diradical 5,5'-bis(1,3,2,4-dithiadiazolyl) [[Formula: see text]-[Formula: see text]] in high yield as a black solid with widely ranging magnetic susceptibilities (e.g., 0.6 to 2.6 μ_B), which on oxidation with AsF₅ regenerated [([Formula: see text])₂][AsF₆]₂. The identity of [[Formula: see text]-[Formula: see text]] was established from EPR, vibrational, and mass spectra. Ab initio molecular orbital [MPW1PW91/6-311G(2df)] calculations show the lowest energy structure to consist of two coplanar rings separated by a C—C single bond (1.444 Å), reflected in the comparison of the vibrational spectra of the diradical with that of [([Formula: see text])₂][AsF₆]₂ and the calculated spectra. Confidence in the calculated [MPW1PW91/6-311G(2df)] structure of the diradical is supported by the excellent agreement between the calculated and X-ray single crystal structure geometries of [[Formula: see text]]₂ and [([Formula: see text])₂]²⁺ in [([Formula: see text])₂][AsF₆]₂. The molecular orbitals indicate the diradical is essentially disjoint, confirmed by a very small (0.07 kJ mol^–1) GVB-PP(TC-SCF)/6-311G* calculated singlet–triplet energy gap. Accordingly, the EPR spectrum of the diradical (in tetrahydrofuran, 293 K) shows a simple 3-line pattern (g = 2.0043, a(¹⁴N) = 1.11 mT) with no observable exchange coupling between the two radical centers. Mechanical grinding of the diradical results in a large increase in paramagnetism (e.g., from 1.03 to 2.55 μ_B) that is unprecedented in main group chemistry. The X-ray diffraction data of the ground and unground powder are consistent with a second order phase change on grinding. Attempts to obtain crystals of the diradical by sublimation led instead to numerous decomposition and rearrangement products, including 4-cyano-1,2,3,5-dithiadiazolyl [NC-[Formula: see text]], monoclinic space group C2/c, a = 9.46(2) Å, b = 7.625(5) Å, c = 13.17(2) Å, β = 107.94(4)°, Z = 8. The structure consists of axially symmetric, co-facial, cis dimers linked to form strands through two sets of C[Formula: see text]N^δ–···S^δ+ contacts. More efficient and larger scale preparations of [SNS][AsF₆] and [([Formula: see text])₂][AsF₆]₂ are reported. Key words: 5,5'-bis(1,3,2,4-dithiadiazolyl), diradical, paramagnetism, mechanical grinding, second order phase change, 4-cyano-1,2,3,5-dithiadiazolyl.

  使用三苯基锑和四丁基铵氯还原[([Formula: see text])₂][As₆]₂，高产率地产生了双自由基5,5'-双(1,3,2,4-二硫杂二氮烷基)[[Formula: see text]-[Formula: see text]]，作为黑色固体，具有广泛的磁化率（例如0.6至2.6μ_B）。在AsF₅氧化下，[[Formula: see text]-[Formula: see text]]再生为[([Formula: see text])₂][AsF₆]₂。通过EPR、振动和质谱确定了[[Formula: see text]-[Formula: see text]]的身份。Ab initio分子轨道[MPW1PW91/6-311G(2df)]计算表明，最低能量结构由两个共面环组成，由C—C单键（1.444 Å）分开，反映在双自由基的振动光谱与[([Formula: see text])₂][AsF₆]₂和计算光谱的比较中。通过[([Formula: see text])₂][AsF₆]₂中[[Formula: see text]]₂和[([Formula: see text])₂]²⁺的计算和X射线单晶结构几何形状的极好一致性，支持双自由基的计算[MPW1PW91/6-311G(2df)]结构的可信度。分子轨道表明，双自由基本质上是不相交的，通过非常小的（0.07 kJ mol^–1）GVB-PP(TC-SCF)/6-311G*计算的单重态–三重态能隙得到确认。因此，双自由基的EPR谱（在四氢呋喃，293 K）显示出简单的3线模式（g = 2.0043，a(¹⁴N) = 1.11 mT），两个自由基中间没有可观测到的交换耦合。机械研磨双自由基导致顺磁性显著增加（例如，从1.03增加到2.55μ_B），这在主族化学中是前所未有的。研磨后的X射线衍射数据与未研磨的粉末一致，表明发生了二阶相变。尝试通过升华获得双自由基的晶体，结果得到了许多分解和重排产物，包括4-氰基-1,2,3,5-二硫杂二氮烷基[NC-[Formula: see text]]，单斜晶系C2/c，a = 9.46(2) Å，b = 7.625(5) Å，c = 13.17(2) Å，β = 107.94(4)°，Z = 8。该结构由轴对称、共面、顺式二聚体组成，通过两组C[Formula: see text]N^δ–···S^δ+接触连接成链。报道了更有效和更大规模的制备[SNS][AsF₆]和[([Formula: see text])₂][AsF₆]₂的方法。关键词：5,5'-双(1,3,2,4-二硫杂二氮烷基)，双自由基，顺磁性，机械研磨，二阶相变，4-氰基-1,2,3,5-二硫杂二氮烷基。
• Brooks, Wendell V. F.; Brownridge, Scott; Parsons, Simon, Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 94, # 1-4, p. 443 - 444
  作者：Brooks, Wendell V. F.、Brownridge, Scott、Parsons, Simon、Passmore, Jack

  DOI：——

  日期：——