1,8-diisocyano-p-menthane | 124493-01-2

• 英文名称: 1,8-diisocyano-p-menthane
• 英文别名: 1,8-diisocyano-p-mentane
• CAS: 124493-01-2
• 化学式: C₁₂H₁₈N₂
• 分子量: 190.288
• InChiKey: OEUHKBMIIZTRLT-KLPPZKSPSA-N

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：

  (苯乙炔基)金 、 1,8-diisocyano-p-menthane 以 二氯甲烷 为溶剂， 以40%的产率得到
  参考文献：
  名称：

  Xiao, Hong; Cheung, Kung-Kai; Che, Chi-Ming, Journal of the Chemical Society, Dalton Transactions, 1996, # 18, p. 3699 - 3704

  摘要：

  DOI：

文献信息

• Chemistry of the Ag₂(dmb)₂²⁺ Template (dmb = 1,8-Diisocyano-<i>p</i>-menthane). Preparation, Characterization, and X-ray Structures of the Ag₂(dmb)₂Y₂ Dimers (Y = NO₃^-, ClO₄^-, CH₃CO₂^-) and the Paramagnetic [Ag₄(dmb)₄(TCNQ)₃]TCNQ Complex (TCNQ = 7,7,8,8-Tetracyanoquinodimethane)
  作者：Daniel Fortin、Marc Drouin、Pierre D. Harvey、F. Geoffrey Herring、David A. Summers、Robert C. Thompson

  DOI：10.1021/ic980974g

  日期：1999.3.1

  S = (3)/(2) and S = (1)/(2) centers for the [Ag(4)(dmb)(4)(TCNQ)(3)](+) and TCNQ(-) moieties, respectively. No hyperfine structure has been observed between 106 and 290 K, indicating the presence of rapid exchange in the paramagnetic system. Crystal data: Ag(2)(dmb)(2)(NO(3))(2), crystal system, orthorhombic, space group = C(cmb), a = 8.6464(15) Å, b = 16.375(3) Å, c = 20.663(5) Å, Z = 4; Ag(2)(dmb)(2)(O(2)CCH(3))(2)

  AgY盐与dmb（1,8-diisocyano-p-menthane）的化学计量比为1：1的直接反应生成双核Ag（2）（dmb）（2）Y（2）络合物。X射线晶体学确定该结构由两个Ag（+）原子组成，两个Ag（+）原子通过形成20元环的两个dmb配体和通过一个O原子中的两个反阴离子桥接，形成四元环（局部对称= D（2）（h）（））。对于Y = NO（3）（-）和CH（3）CO（2）（-），Ag（I）.Ag（I）的间距分别为3.909（1）和3.6831（8）Å。Ag（2）（dmb）（2）Y（2）（Y = NO（3）（-），ClO（4）（-））与LiTCNQ的反应导致顺磁性四核物质[Ag（4）（dmb ）（4）（TCNQ）（3）] TCNQ。在180 K时的结构由两个Ag（2）（dmb）（2）（2+）种类（d（Ag.Ag）= 4.113（1）Å）通过三个平行的TCNQ（-）结合在一起，其中（+）。N＆tbd1;
• Solution and Solid-State Properties of Luminescent M−M Bond-Containing Coordination/Organometallic Polymers Using the RNC-M₂(dppm)₂-CNR Building Blocks (M = Pd, Pt; R = Aryl, Alkyl)
  作者：Jean-François Bérubé、Karl Gagnon、Daniel Fortin、Andreas Decken、Pierre D. Harvey

  DOI：10.1021/ic0509480

  日期：2006.4.1

  Two families of organometallic polymers built upon the bimetallic M2(dppm)2L(2)2+ fragments (M = Pd, Pt; dppm = bis(diphenylphosphino)methane, L = 1,4-diisocyano-2,3,5,6-tetramethylbenzene (diiso), 1,8-diisocyano-p-menthane (dmb), 1-isocyano-2,6-dimethylbenzene, 1-isocyano-4-isopropylbenzene, and tert-butylisocyanide) were synthesized and fully characterized (1H and 31P NMR, X-ray crystallography (model

  基于双金属M2（dppm）2L（2）2+片段构建的两个有机金属聚合物家族（M = Pd，Pt; dppm =双（二苯基膦基）甲烷，L = 1,4-二异氰基-2,3,5,6合成了-四甲基苯（diiso），1,8-二异氰基-对-薄荷烷（dmb），1-异氰基-2,6-二甲基苯，1-异氰基-4-异丙基苯和叔丁基异氰化物（1H和31P NMR，X射线晶体学（模型化合物），IR，拉曼，化学分析，TGA，DSC，粉末XRD，31P NMR T1和NOE，光散射和电导率测量）。固态聚合物的证据来自溶解后聚合物的溶胀和独立膜的形成。但是，这些物质溶解后变成小的低聚物。该材料在298和77 K下以固态发光，在PrK溶液中在77 K下发光。尽管根据芳基异氰化物模型化合物的DFT计算，存在低位的pi-pi * MO水平，但这些排放还是由三重态3（d sigma d sigma *）状态引起的。发射带最大值位于640和750
• Preparation, Spectroscopic Characterization, and Theoretical Study of the [Pd₄(dmb)₄(PPh₃)₂]Cl₂ Complex (dmb = 1,8-Diisocyano-<i>p</i>-menthane) and Its Organometallic Polymer {[Pd₄(dmb)₅](CH₃CO₂)₂}<i>_n</i>:  The First Examples of 58-Electron Linear Pd₄ Clusters
  作者：Tianle Zhang、Marc Drouin、Pierre D. Harvey

  DOI：10.1021/ic9811594

  日期：1999.3.1

  The title compounds [Pd(4)(dmb)(4)(PPh(3))(2)]Cl(2) (1) and [Pd(4)(dmb)(5)](CH(3)CO(2))(2)}(n)() (2) were prepared from the reactions Pd(2)(dba)(3).CHCl(3) + 2dmb + PPh(3) for 1 (dba = dibenzylideneacetone) and Pd(2)(dba)(3).S + excess dmb + Pd(O(2)CCH(3))(2) for 2 (S = benzene or CHCl(3)), in good yields. The stuctures consist of quasi-linear Pd(4)(2+) species (d(PdPd) = 2.524(10), 2.524(10) and

  标题化合物[Pd（4）（dmb）（4）（PPh（3））（2）] Cl（2）（1）和[Pd（4）（dmb）（5）]（CH（3）由反应Pd（2）（dba）（3）制备CO（2））（2）}（n）（）（2）.CHCl（3）+ 2dmb + PPh（3）为1（dba =二苄叉基丙酮）和Pd（2）（dba）（3）.S +过量dmb + 2的Pd（O（2）CCH（3））（2）（S =苯或CHCl（3）），产率高。这些结构由准线性Pd（4）（2+）种类（d（PdPd）= 2.524（10），2.524（10）和2.534（10）Å分别表示为1和2.5973（18），2.6080（18），以及2.6080（18）Å对于2），其中dmb配体桥接Pd原子，形成一个连环。虽然PPh（3）配体轴向协调M（4）结构在1中，第五dmb桥接另一个Pd（4）（dmb）（5）（2+）物种，形成有机金属聚合物。从拉曼光谱法，分别在165和86
• Organometallic Oligomers Based on 1,8-Diisocyano-<i>p</i>-menthane (dmb):  Syntheses and Characterization of the {[M(diphos)(dmb)]BF₄}<i>_n</i> and {[Pd₂(diphos)₂(dmb)](ClO₄)₂}<i>_n</i> Materials (M = Cu, Ag; diphos = dppe, dppp)
  作者：Eric Fournier、Stéphanie Sicard、Andreas Decken、Pierre D. Harvey

  DOI：10.1021/ic034780z

  日期：2004.2.1

  A new strategy to synthesize organometallic oligomers is presented and consists of using the title diisocyanide and chelated metal fragments with bis(diphenylphosphine)alkanes. The title materials are synthesized by reacting the [M(dppe)(BF4)] and [M-2(dppp)(2)](BF4)(2) complexes (M = Cu, Ag; dppe = bis(diphenylphosphino)ethane, dppp = bis(diphenylphosphino)propane) with dmb and the Pd-2-bonded d(9)-d(9) Pd-2(dmb)(2)Cl-2 dimer with dppe or dppp. The model compounds [M(diphos)(CN-t-Bu)(2)]BF4 (M = Cu, Ag) and [Pd-2(diphos)(2)(CN-t-Bu)(2)](ClO4)(2) (diphos = dppe, dppp) have been prepared and characterized as well for comparison purposes. Three of the model compounds were also characterized by X-ray crystallography to establish the diphosphine chelating behavior. The materials are amorphous and have been characterized from the measurements of the intrinsic viscosity, DSC, TGA, and XRD, as well as their capacity for making stand-alone films. The intrinsic viscosity data indicate that the Cu and Pd-2 materials are oligomeric in solution (similar to8-9 units), while the Ag materials are smaller. For [Cu(dppe)(dmb)]-BF4}(n), a glass transition is reproducibly observed at about 82 degreesC (DeltaC(p) = 0.43 J/(g deg)), which suggests that these materials are polymeric in the solid state. The Cu and Ag species are luminescent in the solid state at room temperature exhibiting lambda(max) and tau(e) (emission lifetime) around 480-550 nm and 18-48 mus, respectively, while the Pd-2 species are not luminescent under these conditions. During the course of this study, the unsaturated [M-2-(dppp)(2)](BF4)(2) starting materials (M = Cu, Ag) were prepared, one of which (M = Ag) was characterized by crystallography. The bridging behavior of the dppp ligand in this case contrasts with the chelating behavior seen for the saturated [Cu(dppp)(CN-t-Bu)(2)]BF4 complex.
• Quasi-Unidimensional {[M(dmb)₂]Y}<i>_n</i> Organometallic Polymers (M = Cu(I), Ag(I); dmb = 1,8-Diisocyano-<i>p</i>-menthane; Y = BF₄^-, PF₆^-, NO₃^-, ClO₄^-, CH₃CO₂^-).¹^a Structural, Calorimetric, and Luminescence Properties
  作者：Daniel Fortin、Marc Drouin、Martin Turcotte、Pierre D. Harvey

  DOI：10.1021/ja9600845

  日期：1997.1.1

  A series of new organometallic polymers of the type [M(dmb)(2)]Y}(n) (dmb = 1,8-diisocyano-p-menthane; Y = BF4-, NO3-, ClO4-, M = Cu; Y = BF4-, PF4-, NO3-, CH3CO2-, ClO4-; M = Ag) are reported. These materials have been characterized from single-crystal X-ray diffraction (for [Ag(dmb)(2)]Y}(n); Y = BF4-, NO3-, ClO4-), X-ray powder diffraction (which established the isostructurality between M = Cu and Ag and the relative crystallinity level), differential scanning calorimetry (DSC), solid-state magic spinning angle and solution C-13-NMR, and spin-lattice relaxation time measurements (T-1, C-13-NMR). Three synthesis methods were employed in order to obtain highly crystalline, semicrystalline, and highly amorphous [Cu(dmb)(2)]BF4}(n) polymers. One polymer has been successfully characterized from a light-scattering technique. For the amorphous [Cu(dmb)(2)]BF4}(n) polymer, the molecular weights averaged 160 000. The Ag polymers are found to be rather crystalline and exhibit very low solubility properties. Except for the [Ag(dmb)(2)]PF6}(n) and the highly crystalline [Cu(dmb)(2)]BF4}(n) materials, all polymers exhibit glass transitions in the 37-96 degrees C (305-340 K) range, even if the materials exhibit a very large crystallinity level. The [M(dmb)(2)]Y}(n) organometallic materials (M = Cu, Ag; Y = BF4-, PF6-, NO3-, CH3CO2-) are also strongly luminescent in the visible range (400-600 nm) at 77 K, exhibiting polyexponential emission decay traces (either in the solid state or in solutions). By comparison with the emission properties of the non-polymeric [M(CN-t-Bu)(4)](BF4) compounds (M = Cu, Ag) as a model for a monomeric unit, the first and shea-lived component of the emission decay traces (30-90% in relative intensity) is associated with a higher-energy emission localized at one M center within the polymer (''monomer-like emission''). This is also confirmed by time-resolved emission spectroscopy from the comparision with the emission maxima. The other components in the polyexponential decays are associated with lower-energy emissions that are only present in the polymers. This phenomenon is associated with an energy transfer metal-to-metal delocalized along the M chain somewhat similar to the exciton phenomenon known in organic solids. The depolarization of the emission Light confirms the phenomenon. From density functional theory calculations, the lowest energy excited states have been assigned as MLCT (metal-to-ligand charge transfer) with the HOMO being the M centered d orbitals, and the LUMO being the pi* MO centered on the isocyanide groups. X-ray data for [Ag(dmb)(2)]BF4}(n): space group P2(1)2(1)2(1), orthorhombic, a 9.3273(18) Angstrom, b = 13.685(2) Angstrom, c = 22.124(4) Angstrom, V = 2824.0(9) Angstrom(3), Z = 4, D-calc = 1.353 g/cm(3), R = 0.068, R(w) = 0.073. [Ag(dmb)(2)]-NO3 . 0.70H(2)O}(n): space group P2(1) /c, monoclinic, a = 13.1746(14) Angstrom, b = 9.7475(11) Angstrom, c = 23.207(3) A, beta = 105.15(1)degrees, V = 2876.5(6) Angstrom(3), Z = 4, D-calc = 1.297 g/cm(3), R = 0.051, R(w) = 0.048. [Ag(dmb)(2)]ClO4}(n): space group P2(1)2(1)2(1), orthorhombic, a 9.282(2) Angstrom, b = 13.772(2) Angstrom, c = 22.091(3) Angstrom, V = 2824.1(9) Angstrom(3), Z = 4, D-calc = 1.282 g/cm(3), R = 0.034, R(w) = 0.077.