1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane | 19287-90-2

• 英文名称: 1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane
• 英文别名: closo-1,2-bis(diphenylphosphino)-1,2-carborane；1,2-bis(diphenylphosphino)-ortho-carborane；1,2-bis(diphenylphosphino)-o-carborane；o-carborane-bis-(diphenylphosphine)；bis(diphenylphosphine)-o-carborane；1,2-(PPh2)2-1,2-C2B10H10
• CAS: 19287-90-2
• 化学式: C₂₆H₃₀B₁₀P₂
• 分子量: 512.582
• InChiKey: QCXNYIOLQGUYKS-UHFFFAOYSA-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：

  1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane 在 air 作用下， 以 乙醇 为溶剂， 以69.06%的产率得到1-(OPPh2)-2-(PPH2)-1,2-C2B10H10
  参考文献：
  名称：

  Synthesis and Crystal Structure of Three Carborane Complexes, [M{7,8‐(OPPh ₂ ) ₂ ‐7,8‐C ₂ B ₉ H ₁₀ } ₂ ] (M = Cu, Zn) and [Ni(thf){7,8‐(OPPh ₂ ) ₂ ‐7,8‐C ₂ B ₉ H ₁₀ } ₂ ]·thf, and Two Carborane Compounds, 1‐(OPPh ₂ )‐2‐(PPh ₂ )‐1,2‐C ₂ B ₁₀ H ₁₀ and H[7,8‐(OPPh ₂ ) ₂ ‐7,8‐C ₂ B ₉ H ₁₀ ]·0.25C ₂ H ₅ OH

  摘要：

  AbstractThree new carborane complexes containing the bis(phosphoryl)‐nido‐carborane ligand, [Cu{7,8‐(OPPh2)2‐7,8‐C2B9H10}2] (1), [Zn{7,8‐(OPPh2)2‐7,8‐C2B9H10}2] (2), and [Ni(thf){7,8‐(OPPh2)2‐7,8‐C2B9H10}2]·thf (3), were synthesized by the reactions of 1,2‐(PPh2)2‐1,2‐C2B10H10 with CuCl2·2H2O, ZnCl2, and NiCl2·6H2O, respectively, in ethanol in air. Two other compounds, 1‐(OPPh2)‐2‐(PPh2)‐1,2‐C2B10H10 (4) and H[7,8‐(OPPh2)2‐7,8‐C2B9H10]·0.25C2H5OH (5), were also obtained through the oxidation of the closo ligand in air. All new compounds were characterized by elemental analysis, FT‐IR, 1H and 13C NMR spectroscopy, and single‐crystal X‐ray diffraction. In complexes 1 and 2, the metal atoms are coordinated to the four oxygen atoms of the two bidentate bis(phosphoryl) ligands [7,8‐(OPPh2)2‐7,8‐C2B9H10]– and adopt a square‐planar geometry. For complex 3, the molecular structure reveals that the geometry at the nickel atom is square‐pyramidal, with four oxygen atoms from the four OPPh2 groups and one additional one from a thf molecule. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejic.200600679
• 作为产物：
  描述：

  1,2-dilithio-o-carborane 、 二苯基氯化膦 以 乙醚 为溶剂， 以12.2%的产率得到1,2-bis(diphenylphosphino)-1,2-dicarba-closo-dodecaborane
  参考文献：
  名称：

  的阴离子13顶点直接合成闭合碳-cobaltacarborane簇†

  摘要：

  - 1,2-双（二苯基膦）反应邻-carborane（大号）与[K（THF）{（的Mes边）的Co（η 4 -cod）}]（1，的Mes卞=双（mesityliminoace-环烷）二亚胺，COD = 1,5-环辛二烯），得到阴离子13顶点闭合碳-cobaltacarborane簇（2在一个）步骤。已经通过实验和量子化学技术研究了这种转变的机理，这表明发生了一系列的外球电子转移和异构化过程。这项工作表明，低价金属酸盐阴离子是合成阴离子金属碳硼烷簇的有前途的试剂。

  DOI：

  10.1039/c9dt03111a

文献信息

• Synthesis, Structural Characterization, Ligand Displacement Reaction, and Electrochemical Property of Ruthenium Complexes Incorporating Linked Cyclopentadienyl-Carboranyl Ligands
  作者：Yi Sun、Hoi-Shan Chan、Pierre H. Dixneuf、Zuowei Xie

  DOI：10.1021/om0493816

  日期：2004.11.1

  1,2-bis(diphenylphosphino)ethane), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppm) (1c, dppm = bis(diphenylphosphino)methane), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppf) (1d, dppf = 1,1‘-bis(diphenylphosphino)ferrocene), and [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppc) (1e, dppc = 1,2-(Ph2P)2-1,2-C2B10H10). 1a also reacted with 2,2‘-bipyridine (bipy) to offer [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(bipy) (1f). However, 1a did not react

  用1个当量的合成将[RuCl碳桥连的环戊二烯基配位体碳硼烷的二锂盐的反应2（COD）] X的THF，得到有机钌（II）配合物[ η 5：σ -Me 2 C（ç 5 ħ 4）（ c ^ 2乙10 ħ 10）]钌（COD）（1A），[ η 5：σ -Me 2 C（ç 9 ħ 6）（C 2乙10 ħ 10）]钌（COD）（图2a）和[ η 5：分别为σ- H 2 C（C 13 H 8）（C 2 B 10 H 10）] Ru（COD）（3a）。的治疗1A与THF中的二齿的叔膦，得到相应的COD位移配合物[ η 5：σ -Me 2 C（ç 5 ħ 4）（C 2乙10 ħ 10）]钌（DPPE）（1B，DPPE = 1， 1,2-双（二苯基膦基）乙烷），[ η 5：σ -Me 2 C（C ^ 5 ħ4）（C 2乙10 ħ 10）]钌（DPPM）（1C，DPPM =双（二苯基膦基）甲烷），[ η 5：σ
• Tunable from Blue to Red Emissive Composites and Solids of Silver Diphosphane Systems with Higher Quantum Yields than the Diphosphane Ligands
  作者：María Calvo、Olga Crespo、M. Concepción Gimeno、Antonio Laguna、M. Teresa Oliván、Víctor Polo、Diego Rodríguez、Jose-M. Sáez-Rocher

  DOI：10.1021/acs.inorgchem.0c02238

  日期：2020.10.5

  (PR2)2C2B10H10 (R = Ph and iPr)] display the whole palette of colors from blue to red upon selection of the anionic ligand (X) and the diphosphane (P–P). The diphosphane seems to play the most important role in tuning the emission energy and thermally activated delayed fluorescence (TADF) behavior. The PMMA composites of the complexes exhibit higher quantum yields than that of the diphosphane ligands and those with

  PMMA复合物和固体式[AgX（P–P）] n [ n = 1和2; X ＝ Cl，NO 3，ClO 4，CF 3 COO和OTf；P–P = dppb，黄药，（PR 2）2 C 2 B 10 H 10（R = Ph和iPr）]显示了选择了阴离子配体（X）和二膦（P–P）时从蓝色到红色的整个调色板。在调节发射能量和热激活延迟荧光（TADF）行为方面，二膦似乎起着最重要的作用。配合物的PMMA复合物比二膦配体具有更高的量子产率，而具有dppb的那些则在28％至53％之间。值得注意的是，取代硬质相中占主导地位的二氧化银银配合物的蓝绿色发射，具有碳硼烷二膦的那些是黄橙色或橙红色发射体。对于P–P = dppb，X = Cl的配合物进行了理论研究。P–P = dppic，X = NO 3；P–P = dppcc，X = Cl，NO 3，OTf和单核络合物[AgX（xantphos）]（X = Cl
• The formation of nido [7,8-(PR2)2-7,8-C2B9H10]− from closo 1,2−(PR2)2−1,2−C2B10H10 (): a process enhanced by complexation
  作者：Francesc Teixidor、Clara Viñas、M.Mar Abad、Raikko Kivekäs、Reijo Sillanpää

  DOI：10.1016/0022-328x(95)05809-4

  日期：1996.3

  directly connected to the carborane cage, the coordination behavior of phosphorus atoms directly bonded to the cage has been studied. The reactivity of bisphosphines [7,8−(PR2)2−7,8−C2B9H10]− () has been investigated. These new chelating ligands exhibit some similarities to the much used 1,2-diphenylphosphinoethane (diphos), such as the spacing between the two phosphorus atoms, and their five-membered ring

  为了深入了解直接连接到碳硼烷笼中的富电子元素的相互影响，已经研究了直接键合到笼中的磷原子的配位行为。双膦类[7,8-（PR 2）2 -7,8-C 2 B 9 H 10 ] -（）已被调查。这些新的螯合配体与经常使用的1,2-二苯基膦基乙烷（diphos）有一些相似之处，例如两个磷原子之间的间隔以及它们的五元环螯合能力，但存在显着差异，并且连接特性不同。预期的。差异主要归因于结合的碳硼烷簇，可以总结如下：（1）配体是阴离子的；（2）磷原子呈偏光构象；（3）与金属的B（3）-H配位是可能的。研究的部分降解闭合碳簇到巢络合增强集群，几种金属配合物与处理过的闭合碳在乙醇配体。[AuCl的晶体结构2 7,8-（P（i Pr 2）2 -7,8-C 2 B 9 H 10 }]和[RuCl 2 7,8-（P（i Pr 2）2 -7,8-C 2 B 9 H 10 } 2 ]已经确定。
• Long-Lived Excited States of Zwitterionic Copper(I) Complexes for Photoinduced Cross-Dehydrogenative Coupling Reactions
  作者：Bin Wang、Deepak Prakash Shelar、Xian-Zhu Han、Ting-Ting Li、Xiangguo Guan、Wei Lu、Kun Liu、Yong Chen、Wen-Fu Fu、Chi-Ming Che

  DOI：10.1002/chem.201405356

  日期：2015.1.12

  copper(I) complexes containing phenanthroline and monoanionic nido‐carborane‐diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X‐ray diffraction. These complexes exhibit intense absorptions in the visible range and excited‐state lifetimes on the microsecond scale. Their application in visible‐light‐induced cross‐dehydrogenative coupling reactions

  制备了四种含有邻菲咯啉和单阴离子的Nido-碳硼烷-二膦配体的杂铜（I）配合物，并通过各种光谱技术和X射线衍射对其结构进行了表征。这些络合物在可见光范围内表现出强烈的吸收，并在微秒级上具有激发态寿命。研究了它们在可见光诱导的交叉脱氢偶联反应中的应用。初步研究表明，四种铜（I）配合物之一是使用氧作为氧化剂进行光诱导的氧化CH官能化的有效催化剂。此外，通过对我们的Cu I混合物进行光照射（λ > 420 nm）以良好的优异产率获得了α-官能化的叔胺。复杂的叔胺和各种亲核试剂（硝基烷，丙酮或吲哚）在有氧条件下。电子顺磁共振测量提供了在这些光催化反应中形成超氧自由基阴离子（O 2 -⋅）而不是单线态氧（1 O 2）的证据。
• Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity
  作者：Xian-Kuan Huo、Ge Su、Guo-Xin Jin

  DOI：10.1039/b918272a

  日期：——

  The neutral Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) and zwitterionic Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9) (Cp* = η5-C5Me5, M = Ir, Rh, 1-PPh2-2-S-1,2-C2B10H10 = [1-(diphenylphosphino)-2-thiolato)-1,2-dicarba-closo-carborane], 3-OCH3-7-PPh2-8-S-7,8-C2B9H9 = [3-(methoxyl)-7-(diphenylphosphino)-8-(thiolato)-7,8-dicarba-nido-carborane]−) were synthesized and fully characterized. The 18-electron neutral closo-carborane complexes Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) (M = Ir (1a), Rh (1b)) can be easily deboronated to result in the formation of reactive 16-electron zwitterionic nido-carborane complexes [Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9)] (M = Ir (2a), Rh(2b)). The oxidation of 2b with O2 gas afforded the corresponding sulfone complex 3b in high yields. Utilization of its unsaturated feature in 16-electron zwitterionic nido-carborane complexes offers a potential strategy to synthesize new types of organometallic complexes.

  合中性化合物 Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10) 和带电双重离子化合物 Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9)（Cp* = η5-C5Me5，M = Ir，Rh，1-PPh2-2-S-1,2-C2B10H10 = [1-(二苯基膦基)-2-硫醇基)-1,2-二碳烷-closo-卡波烯]，3-OCH3-7-PPh2-8-S-7,8-C2B9H9 = [3-(甲氧基)-7-(二苯基膦基)-8-(硫醇基)-7,8-二碳烷-nido-卡波烯]−）已合成并进行了全面表征。18电子中性closo-卡波烯配合物 Cp*M(Cl)(1-PPh2-2-S-1,2-C2B10H10)（M = Ir (1a)，Rh (1b)）可以轻易去硼，形成具有反应性的16电子带电双重离子 nido-卡波烯配合物 [Cp*M(3-OCH3-7-PPh2-8-S-7,8-C2B9H9)]（M = Ir (2a)，Rh(2b)）。用O2气体氧化2b可获得相应的磺酰复合物3b，产率很高。利用其在16电子带电双重离子nido-卡波烯配合物中的去饱和特性，为合成新类型的有机金属配合物提供了一种潜在的策略。