Ni(dppv)Cl2 | 42584-04-3

• 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: Ni(dppv)Cl2
• 英文别名: (dppv)NiCl₂
• CAS: 42584-04-3
• 化学式: C₂₆H₂₂Cl₂NiP₂
• 分子量: 526.004
• InChiKey: OBYNXQPCEJCWSB-FAIYXUOWSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  Ni(dppv)Cl2 在 chlorine 作用下， 以 四氯化碳 为溶剂， 生成 NiCl3(cis-bis(diphenylphosphino)ethylene)
  参考文献：
  名称：

  Gray, Leslie R.; Higgins, Simon J.; Levason, William, Journal of the Chemical Society, Dalton Transactions, 1984, p. 459 - 468

  摘要：

  DOI：
• 作为产物：
  描述：

  NiCl3(cis-bis(diphenylphosphino)ethylene) 以 二氯甲烷 为溶剂， 生成 Ni(dppv)Cl2
  参考文献：
  名称：

  由二级配位球实现的单体镍（III）配合物的卤素光消除

  摘要：

  Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.

  DOI：

  10.1021/acs.organomet.5b00568

文献信息

• Synthesis, Structure, and Reactivity of 13-Vertex Carboranes and 14-Vertex Metallacarboranes
  作者：Liang Deng、Hoi-Shan Chan、Zuowei Xie

  DOI：10.1021/ja0605772

  日期：2006.4.1

  moisture. The 13-vertex closo-carboranes were readily reduced by groups 1 and 2 metals. Accordingly, several 13-vertex nido-carborane dianionic salts [nido-1,2-(CH2)3-1,2-C2B11H11][Li2(DME)2(THF)2] (13), [[nido-1,2-(CH2)3-1,2-C2B11H11][Na2(THF)4]]n (13a), [[nido-1,2-(CH2)3-3-Ph-1,2-C2B11H10][Na2(THF)4]]n (14), [[nido-1,2-C6H4(CH2)2-1,2-C2B11H11][Na2(THF)4]]n (15), and [nido-1,2-(CH2)3-1,2-C2B11H11][M(THF)5]

  报告了 13 顶点 closo- 和 nido-carboranes 的合成、性质和合成应用。氨基碳硼烷盐 [(CH2)3C2B10H10]Na2 与二卤硼烷试剂反应得到 13-顶点 closo-carboranes 1,2-( )3-3-R-1,2-C2B11H10 (R = H (2), Ph (3), Z-EtCH=C(Et) (4), E-(t)BuCH=CH (5))。用 HBBr2.SMe2 处理蛛网膜碳硼烷盐 [( )3C2B10H10]Li4 得到 13 顶点碳硼烷 2 和 14 顶点闭环碳硼烷 ( )3C2B12H12 (8)。另一方面，[ ( )2C2B10H10]Li4 与 HBBr2.SMe2 的反应仅生成一个 13 顶点的 closo-carborane 1,2-C6H4( )2-1,2-C2B11H11 (9)。在催化量的 AlCl3 存在下，2
• Synthesis of (diphosphine)Ni-bridged double-butterfly Fe/S cluster complexes and isolation of the reactive μ-CO-containing anionic Fe/S cluster intermediates
  作者：Li-Cheng Song、Ling Li、Yuan-Yuan Hu、Hai-Bin Song

  DOI：10.1016/j.jorganchem.2013.06.043

  日期：2013.10

  A new series of (diphosphine)Ni-bridged double-butterfly Fe/S clusters [(μ-RS)(μ-SCS)Fe2(CO)6]2[Ni(diphosphine)] (1–6, R = p-MeC6H4, Ph, n-Bu; diphosphine = dppe, dppv, dppb, dppf) was prepared by a new type of sequential reactions of the μ-CO-containing anions [(μ-RS)(μ-CO)Fe2(CO)6]− (type A anions, generated in situ from Fe3(CO)12, RSH, and Et3N) with excess CS2, followed by treatment of the resulting

  一个新的（二膦）镍桥双蝶Fe / S簇[[μ-RS ] [μSCS ] Fe 2（CO）6 ] 2 [Ni（二膦）]（1 – 6，R =  p -MeC 6 H 4，Ph，n -Bu;二膦= dppe，dppv，dppb，dppf）是通过新型的含μ-CO阴离子的顺序反应制备的[[μ-RS）（μ-CO ）Fe 2（CO）6 ] -（A型阴离子，由Fe 3（CO）12，RSH和Et 3 N原位产生）带有过量的CS 2，接着处理所得到的μ-CS的2含阴离子[（μ-RS）（μ-S CS）的Fe 2（CO）6 ] - （式乙阴离子）与各种（二膦）的NiCl 2络合物。此外，两种A型阴离子，即[（μ- p -MeC 6 H 4 S）（μ-CO）Fe 2（CO）6 ] -（A 1）和[（μ-PhS）（μ-成功分离出CO）Fe 2（CO）6 ] -（A 2）作为它们的[Et 3 NH]+和[Ph 4 P]
• Synthesis, Structures, and Properties of 1,2,4,5-Benzenetetrathiolate Linked Group 10 Metal Complexes
  作者：Kuppuswamy Arumugam、Mohamed C. Shaw、P. Chandrasekaran、Dino Villagrán、Thomas G. Gray、Joel T. Mague、James P. Donahue

  DOI：10.1021/ic901257s

  日期：2009.11.16

  stable with Na[BArF24] (BArF24 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), suggesting that the radical cation generated by oxidation is vulnerable to reaction with PF6−. Chemical oxidation of 3d with [Cp2Fe][BArF24] leads to formation of [3d][BArF24]. Structural identification of [3d][BArF24] reveals appreciable shortening and lengthening of C−S and C−C bond distances, respectively, within the

  双金属化合物[（P-P）M（S 2 C 6 H 2 S 2）M（P-P）]（M = Ni，Pd; PP =螯合双（膦），3a - 3f）由O 3制备。 CS 2 ç 6 ħ 2小号2 C = O或ñ卜2周的SnS 2 c ^ 6 ħ 2小号2的Sn ñ卜2，其被保护的1,2,4,5- benzenetetrathiolate的形式。O═CS的选择性monodeprotections 2 c ^ 6 ħ 2小号2 C = O或Ñ卜2周的SnS 2 c ^ 6 ħ 2小号2的Sn Ñ卜2引线为[（P-P）的Ni（S 2 c ^ 6 ħ 2小号2 C = O）]或[（P-P）的Ni（š 2 ç 6 H 2 S 2 Sn n Bu 2）]；前者用于制备三金属化合物[（dcpe）Ni（S 2 C 6 H 2 S 2）M（S 2 C 6 H 2 S 2）Ni（dcpe）]（M = Ni（6a）或Pt（6b）；dcpe
• Nickel(II), palladium(II), platinum(II) and platinum(IV) complexes of cis-1,2-bis(diphenylphosphino) ethene and nitrogen-containing heterocycles or sulfur ligands
  作者：Werner Oberhauser、Christian Bachmann、Thomas Stampfl、Rainer Haid、Christoph Langes、Alexander Rieder、Peter Brüggeller

  DOI：10.1016/s0020-1693(97)06041-6

  日期：1998.6

  anhydrous Na2S give the trinuclear complexes [M3(μ3-S)2(cis-dppen)3]X2 (M=Ni, X−=PF6 (6); M=Pd, X−=BF4 (7)). In the case of 1 Na2S · 9H2O is needed to produce the corresponding Pt(II) complex [Pt3(μ3-S)2(cis-dppen)3] Cl2 (8). Interestingly, treatment of [NiCl2(cis-dppen)] with S2CPCy3 leads to the unexpected mononuclear compound [Ni(CS2)4(cis-dppen)] (BF4)2 (9). Oxidation of [Pt(cis-dppen)2]Cl2 by chlorine

  制备了几种新型的含双膦配体顺式-1,2-双（二苯基膦基）乙烯（顺式-dppen）的Ni（II），Pd（II），Pt（II）和Pt（IV）配合物，并通过X-进行了表征射线衍射法。NMR光谱（195 Pt 1 H}，31 P 1 H，13 C 1 H}，1 H），快速原子轰击质谱，IR光谱，元素分析和熔点。在[PtCl 2（顺式-dppen）]（1）的情况下，发现了第二种晶体修饰形式，并明确地通过X射线结构分析进行了表征：单斜晶系。P 2 1 /Ñ，ž = 4，一个= 8.312（1），b = 14.578（2），C ^ = 19.868（4），β = 91.27（1）°，[R = 0.028对于3862米观察到的反射（我> 3 σ（我））。与先前报道的1的另一种修饰的X射线结构相反，后者显示了配位面和乙烯桥的完全共面性，而在1的第二种修饰中，这种共面性受到晶体堆积效应的轻微干扰。
• Five-membered ring chelate complexes of Ni(II), Pd(II) and Pt(II) derived of di-(2-pyridyl)-N-ethylimine
  作者：Noemí Andrade-López、Tracy A. Hanna、José G. Alvarado-Rodríguez、Adriana Luqueño-Reyes、Bernat A. Martínez-Ortega、Daniel Mendoza-Espinosa

  DOI：10.1016/j.poly.2010.04.029

  日期：2010.7

  the complexes 3 and 4 were characterized in solution by NMR. In addition, solid state structures of compounds 1–4 were determined using single crystal X-ray diffraction analyses. X-ray diffraction data of the complexes 3 and 4 showed a distorted square planar local geometry at palladium and platinum atoms with the chlorine atoms in a cis-coordination; in 2 a local octahedral geometry at nickel atom

  摘要由二-（2-吡啶基）-N-乙基亚胺（1）与[NiCl2dppe]反应制得顺式双[二（2-吡啶基）-N-乙基亚胺}氯化镍（II）[ dppe =在热乙腈中的比例为2：1的顺式-1,2-双（二苯基膦基）乙烯]。获得了顺二氯二（2-吡啶基）-N-乙基亚胺}钯（II）（3）和顺二氯二（2-吡啶基）-N-乙基亚胺}铂（II）（4）配合物由MCl2（M = Pd，Pt）和（1）在热乙腈中以等摩尔比反应制得。通过红外光谱，元素分析和质谱对化合物1-4进行了表征。配合物3和4在溶液中通过NMR表征。此外，使用单晶X射线衍射分析确定了化合物1-4的固态结构。配合物3和4的X射线衍射数据表明，在钯和铂原子处，氯原子呈顺式配位，方形平面局部几何形状失真。在2中，观察到镍原子处的局部八面体几何形状。配合物3和4被安排为二聚体，M⋯M距离分别为3.4567（4）A（M = Pd）和3.4221（4）A（M =