bis(boranatodiphenylphosphonio)methane | 24442-15-7

• 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: bis(boranatodiphenylphosphonio)methane
• 英文别名: (bis(diphenylphosphanyl)methane)(BH3)2；methylenebis(diphenylphosphane)-borane(1:2)；dppm(BH3)2；H2C(PPh2BH3)2；(bis(diphenylphosphanyl)methane)(borane)2；[[Boranuidyl(diphenyl)phosphaniumyl]methyl-diphenylphosphaniumyl]boranuide；[[boranuidyl(diphenyl)phosphaniumyl]methyl-diphenylphosphaniumyl]boranuide
• CAS: 24442-15-7
• 化学式: C₂₅H₂₈B₂P₂
• 分子量: 412.067
• InChiKey: VCKOVDOQHGOJDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(boranatodiphenylphosphonio)methane 以 正己烷 为溶剂， 反应 0.5h， 生成 K{CH(PPh2BH3)2}(N,N,N′,N′,N″-pentamethyldiethylenetriamine)2
  参考文献：
  名称：

  Synthesis, characterization and reactivity of potassium and barium complexes containing phosphane–borane stabilized methanides

  摘要：

  制备了聚合钾配合物[K{CH(PPh2BH3)2}]-(1)，并用作合成相关N,N,N-2,N-四甲基乙二胺(tmeda)和N,N,N‐2,N‐‐2,N‐‐‐‐‐五甲基二亚乙基三胺 (pmdta) 连接钾衍生物 [K{CH(PPh2BH3)2}(tmeda)2]‐ (2) 和 [K{CH (PPh2BH3)2}(pmdta)]2 (3)。与 [BaI2(thf)5] 的盐复分解反应可以合成钡衍生物 [BaI{CH(PPh2BH3)2}(thf)5] (5) 和 [Ba{CH(PPh2BH3)2}2(solv)2 }] (solv = Et2O, thf) (6)，比钾衍生物更容易发生后续反应。分离出所得产物之一[Ba4O{CH(PPh2BH3)2}3{Ph2PCH(BH3)PPh2BH3}3] (7)，其包含Ph2PCHPh2双(硼烷)加合物的两种不同异构形式。通过核磁共振技术和单晶 X 射线衍射测量对配合物进行了表征。

  DOI：

  10.1039/c3dt52257a
• 作为产物：
  描述：

  双二苯基膦甲烷 在 dimethyl sulfide borane 、 氯化铵 作用下， 以 二氯甲烷 、 水 为溶剂， 以94%的产率得到bis(boranatodiphenylphosphonio)methane
  参考文献：
  名称：

  Catalyst-free alcoholysis of phosphane-boranes: a smooth, cheap, and efficient deprotection procedure

  摘要：

  Catalyst-free alcoholytic deprotection of borane-protected phosphorus compounds offers a smooth, efficient, and clean alternative to existing deprotection methods. In this paper we report our results on the general applicability of deprotecting phosphane- and phosphite-borane adducts by means of simple alcoholysis without the use of molecular sieves as a catalyst. Phosphane-boranes bearing at least one aromatic substituent are readily deprotected in high yields. Borane complexes of trialkylphosphanes or phosphites, however, cannot be deprotected in this way. The main merit of our method is its simplicity: apart from evaporation of the solvent, no further work-up or purification is needed. (C) 2009 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2009.05.063

文献信息

• Tris(borane) Adducts of Diphosphanylmethanides: The [H ₃ BCH(PPh ₂ BH ₃ ) ₂ ] ^– Anion and Its Alkali Metal Complexes
  作者：Jens Langer、Robert Geitner、Helmar Görls

  DOI：10.1002/ejic.201402845

  日期：2014.12

  BH3·SMe2 in toluene resulted in the formation of the novel compound [(LiH3BCH(PPh2BH3)2})∞] (2). The subsequent addition of ethereal ligands led to the isolation of [LiH3BCH(PPh2BH3)2}(Me4thf)] (3) and [LiH3BCH(PPh2BH3)2}(thf)3] (4). Treatment of these complexes with stronger Lewis bases such as N,N,N′,N′-tetramethylethane-1,2-diamine (tmeda) results in the removal of one phosphorus-bound BH3 molecule

  研究了含有硼烷修饰的二膦基甲烷配体 [CH(PPh2BH3)2]– 的锂配合物对 BH3 的不同路易斯碱加合物的反应性，以进一步了解该衍生物异构化的机理，该异构化是通过转变形式进行的一个 BH3 基团从磷原子到碳原子。而在 THF 中使用 BH3·THF 仅导致起始材料的 thf 加合物，[LiCH(PPh2BH3)2}(thf)2] (1)，BH3·SMe2 在甲苯中的应用导致形成新化合物 [(LiH3BCH(PPh2BH3)2})∞] (2)。随后添加醚配体导致 [LiH3BCH(PPh2BH3)2}(Me4thf)] (3) 和 [LiH3BCH(PPh2BH3)2}(thf)3] (4) 的分离。用更强的路易斯碱如 N,N,N',N'-tetramethylethane-1 处理这些配合物，2-二胺 (tmeda) 导致去除一个与磷结合的 BH3 分子并形成 [Ph2PCH(BH3)PPh2BH3]–
• Bonding mode of a new bis-phosphine-borane alkyl ligand to a Rh(i) species
  作者：Matthias Blug、Dan Grünstein、Gilles Alcaraz、Sylviane Sabo-Etienne、Xavier-Frederic Le Goff、Pascal Le Floch、Nicolas Mézailles

  DOI：10.1039/b907813d

  日期：——

  The stoichiometric reaction of [Rh(COD)Cl]2 with the anion resulting from the deprotonation of dppm(BH3)2 yielded a new alkyl Rh(I) complex; the coordination modes of the BH3groups are discussed on the basis of X-ray data, variable temperature multinuclear NMR experiments and DFT studies.

  Rh(COD)Cl]2 与 dppm(BH3)2 去质子化产生的阴离子发生了化学反应，生成了一种新的烷基 Rh(I) 复合物；根据 X 射线数据、变温多核核磁共振实验和 DFT 研究讨论了 BH3 基团的配位模式。
• Calcium carbene complexes with boranophosphorano side-arms: CaC[P(Ph)2BH3]2
  作者：Lars Orzechowski、Georg Jansen、Martin Lutz、Sjoerd Harder

  DOI：10.1039/b823224e

  日期：——

  The ligand H2C(PPh2BH3)2 (4-H2) reacted with one or a half equivalent of (para-tBu-C6H4CH2)2Ca·(THF)4 to form the calcium complexes Ca[HC(PPh2BH3)2]2 (4-H)2Ca and CaC(PPh2BH3)2 (4-Ca), respectively. The crystal structures of their THF adducts (4-H)2Ca·THF and [4-Ca·(THF)]2 follow the same trends as observed for the corresponding iminophosphorano substituted complexes Ca[HC(PPh2NR)2]2 and [CaC(PPh2NR)2]2. The P–C bonds shorten upon gradual deprotonation, whereas the P–B and P–N bonds elongate. The geometries of DFT-optimized model systems and complete molecular structures show similar trends. Also the charge distribution within the boranophosphorano complexes is similar to that in the iminophosphorano complexes. The high positive charges on Ca (1.74–1.75) indicate a predominantly ionic ligand–Ca bonding. High negative charges on the central carbon atom (−1.103 in Ca[HC(PH2BH3)2]2 and −1.775 in [CaC(PH2BH3)2]2) compare well to those calculated for analogous iminophosphorano complexes (−1.126 Ca[HC(PH2NH)2]2 and −1.847 [CaC(PH2NH)2]2, respectively). Thus, in both types of complexes delocalization of electron density over the boranophosphorano or iminophosphorano substituents does not play a major role. Complex [4-Ca·(THF)]2 does not react with adamantyl cyanide. Instead the adduct (4-Ca)2·(THF)·(adamantyl-CN) formed (a crystal structure has been determined).

  配体 H2C(PPh2BH3)2 (4-H2) 与一或半当量的 (para-tBu-C6H4CH2)2Ca·(THF)4 反应形成钙络合物 Ca[HC(PPh2BH3)2]2 (4-分别为 H)2Ca 和 CaC(PPh2BH3)2 (4-Ca)。它们的 THF 加合物 (4-H)2Ca·THF 和 [4-Ca·(THF)]2 的晶体结构遵循与相应亚氨基磷取代配合物 Ca[HC(PPh2NR)2]2 和 [CaC] 相同的趋势(PPh2NR)2]2。 P-C 键随着逐渐去质子化而缩短，而 P-B 和 P-N 键则延长。 DFT 优化模型系统和完整分子结构的几何形状显示出相似的趋势。此外，硼杂正膦配合物内的电荷分布与亚氨基正膦配合物中的电荷分布相似。 Ca 上的高正电荷 (1.74–1.75) 表明主要是离子配体-Ca 键合。中心碳原子上的高负电荷（Ca[HC(PH2BH3)2]2 中为 -1.103 和 [CaC(PH2BH3)2]2 中为 -1.775) 与类似亚氨基磷配合物的计算结果 (-1.126 Ca[HC( PH2NH)2]2 和 -1.847 [CaC(PH2NH)2]2 分别)。因此，在两种类型的配合物中，硼烷正膦或亚氨基正膦取代基上的电子密度离域并不起主要作用。络合物[4-Ca·(THF)]2 不与金刚烷基氰反应。相反，形成加合物(4-Ca)2·(THF)·(金刚烷基-CN)（晶体结构已确定）。
• Synthesis and crystal structures of bis(diphenylphosphanyl)methanides of lithium and calcium as well as of their borane adducts
  作者：Jens Langer、Katja Wimmer、Helmar Görls、Matthias Westerhausen

  DOI：10.1039/b822530c

  日期：——

  LiHC(PPh(2))(2)}, which forms [(tmeda)(thf)LiHC(PPh(2))(2)}] () in the presence of appropriate Lewis bases, with KOtBu and CaI(2) in THF yields [(thf)(3)CaCH(PPh(2))(2)}(2)] (). In complexes and the bis(diphenylphosphanyl)methanide anions act as bidentate ligands via the phosphorus atoms. Lithiation of H(2)C(PPh(2)-BH(3))(2) in diethyl ether leads to the formation of [(Et(2)O)(2)LiCH(PPh(2)-BH(3))(2)}]

  Li HC（PPh（2））（2）}在适当的路易斯碱的存在下形成[（tmeda）（thf）Li HC（PPh（2））（2）}]（）的反应，用KOtBu和CaI（2）在THF中制得[（thf）（3）Ca CH（PPh（2））（2）}（2）]（）。在络合物中，双（二苯基膦基）甲烷阴离子通过磷原子充当双齿配体。H（2）C（PPh（2）-BH（3））（2）在乙醚中的锂化导致[[Et（2）O）（2）Li CH（PPh（2）-BH （3））（2）}]（）可以从1,2-二甲氧基乙烷（DME）重结晶，导致形成溶剂分离的[（dme）（3）Li]（+）[HC（PPh（2） ）-BH（3））（2）]（-）（'）。与KOtBu反应，然后与无水CaI（2）反应产生[（thf）Ca CH（PPh（2）-BH（3））（2）}（2）]（）。在化合物中，在固态状态下观察到的Ca-C键为2.754（3）A，仅与一个阴
• Phosphine−Boranes as Bidentate Ligands:  Formation of [8,8-η²-{η²-(BH₃)·dppm}-<i>n</i><i>ido</i>-8,7-RhSB₉H₁₀] and [9,9-η²-{η²-(BH₃)·dppm}-<i>n</i><i>ido</i>-9,7,8-RhC₂B₈H₁₁] from [8,8-(η²-dppm)-8-(η¹-dppm)-<i>n</i><i>ido</i>-8,7-RhSB₉H₁₀] and [9,9-(η²-dppm)-9-(η¹-dppm)-<i>n</i><i>ido</i>-9,7,8-RhC₂B₈H₁₁], Respectively
  作者：Oleg Volkov、Ramón Macías、Nigam P. Rath、Lawrence Barton

  DOI：10.1021/ic0258375

  日期：2002.11.1

  two clusters [8,8-(eta(2)-dppm)-8-(eta(1)-dppm)-nido-8,7-RhSB(9)H(10)] (1) and [9,9-(eta(2)-dppm)-9-(eta(1)-dppm)-nido-9,7,8-RhC(2)B(8)H(11)] (2) (dppm = PPh(2)CH(2)PPh(2)), both of which contain pendant PPh(2) groups, react with BH(3).thf to afford the species [8,8-eta(2)-(eta(2)-(BH(3)).dppm)-nido-8,7-RhSB(9)H(10)] (3) and [9,9-eta(2)-(eta(2)-(BH(3)).dppm))-nido-9,7,8-RhC(2)B(8)H(11)] (4), respectively

  两个簇[8,8-（eta（2）-dppm）-8-（eta（1）-dppm）-nido-8,7-RhSB（9）H（10）]（1）和[9， 9-（eta（2）-dppm）-9-（eta（1）-dppm）-nido-9,7,8-RhC（2）B（8）H（11）]（2）（dppm = PPh （2）CH（2）PPh（2））都包含PPh（2）侧基，与BH（3）.thf反应，得到种类[8,8-eta（2）-（eta（2） ）-（BH（3））。dppm）-nido-8,7-RhSB（9）H（10）]（3）和[9,9-eta（2）-（eta（2）-（BH（ 3））。dppm））-nido-9,7,8-RhC（2）B（8）H（11）]（4）。这两个物种非常相似，因为它们都包含双齿配体[（BH（3））。dppm]，该配体通过PPh（2）和eta（2）-BH（3）与Rh中心配位）组。因此，BH（3）基团中的B原子