diiodotriethylphosphorane | 98961-77-4

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: diiodotriethylphosphorane
• 英文别名: triethyl-diiodo-phosphorane；Triaethyl-dijod-phosphoran；Triethyl(diiodo)-lambda5-phosphane；triethyl(diiodo)-λ5-phosphane
• CAS: 98961-77-4
• 化学式: C₆H₁₅I₂P
• 分子量: 371.968
• InChiKey: XUIARSAPYBFQPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  diiodotriethylphosphorane 、 镍 以 乙醚 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  Inorganic grignard analogues. Reaction of nickel powder with dihalogenotriorganophosphorus compounds to form nickel-(II) and -(III) phosphine complexes; isolation of planar [Ni(PPh3)I3]? and the crystal structure of [Ni(PPhMe2)2Br2]

  摘要：

  Reactions of dihalogenotriorganophosphorus compounds R3PX2 (X = Br or I) with unactivated coarse-grain nickel metal powder have been investigated. The nature of the nickel phosphine complexes formed is remarkably dependent on both R and X. Where R not-equal Me and X = I the nickel(II) complexes [R3PI] [Ni(PR3)I3] are formed, analogous to, but not isostructural with, similar cobalt complexes of the same stoichiometry formed from cobalt powder and R3PI2. Quantitative electronic spectroscopic studies indicated that, surprisingly, the [R3PI][Ni(PR3)I3] complexes all have predominantiy square-planar geometry around nickel. Where R = Me and X = 1, the nickel(III) complex [Ni(PMe3)2I3] is obtained in quantitative yield, the other product being diiodine. Reaction of nickel powder with Me2PhPI2 yields both the nickel(II) complex, [MePhPI][Ni(PPhMe2)I3], and the nickel(III) complex, [Ni(PPhMe2)2I3]. These observations again mirror analogous cobalt reactions. Reaction of the analogous dibromo compounds, R3PBr2, with nickel powder is extremely sensitive to the nature of R. Where R = Me, Et or Pn(n) no reaction occurs; where R3 = PhMe2 the square-planar complex [Ni(PPhMe2)2Br2] and an octahedral complex of stoichiometry Ni(PPhMe2)2Br, are obtained in equal yield. Where R3 = Ph2Pr(n) the octahedral complex [Ni(PPh2Prn)2Br4] is formed with a trace of the planar complex [Ni(PPh2Prn)2Br2], and where R = Ph the octahedral complex [Ni(PPh3)2Br4] is formed in quantitative yield. The complex [Ni(PPhMe2)2Br] has been crystallographically characterised: monoclinic, space group P2(1)/a, a = 10.018(2), b = 10.249(1), c = 10.138(1) angstrom and Z = 2 (molecule centrosymmetric).

  DOI：

  10.1039/dt9930002875
• 作为产物：
  描述：

  三乙基膦 在 碘 作用下， 生成 diiodotriethylphosphorane
  参考文献：
  名称：

  Zur Konstitution und Solvolyse von terti�ren Phosphindihalogeniden ? R3PX2 ?

  摘要：

  AbstractElementares Chlor, Brom und Jod reagieren unter geeigneten Bedingungen mit aliphatischen, hydroaromatischen und aromatischen tertiären Phosphinen im Mol‐Verh. 1:1. Die Additionsverbindungen sind mit Ausnahme des (C6H11)3PJ2 und (C6H5)3PJ2 äußerst feuchtigkeitsempfindlich. Auf Grund ihres salzartigen Verhaltens können sie als Phosphoniumsalze aufgefaßt werden.Die Phosphindihalogenide setzen sich mit SbCl5, SbBr3 und HgJ2 im Sinne einer Halogen‐Donator‐Akzeptor‐Reaktion um. Die dabei entstehenden Phosphoniumsalze zeigen die Leitfähigkeiten binärer Elektrolyte. Sie enthalten das Phosphoniumkation [R3PX]+. Während Phosphindichloride und Phosphindibromide in Lösung mehr als Neutralmolekeln vorliegen, wird für Phosphindijodide in Lösung eine Dissoziation in [R3PJ]+ und J−‐Ionen bewiesen.Aus Phosphindihalogeniden und Reinecke‐Salz können in wäßrigem Alkohol Phosphinoxyd‐Reinecke‐Säure‐Additionsverbindungen im Verhältnis 1:1, 2:1 und 4:1 dargestellt werden. Bei der Solvolyse von Tricyclohexylphosphindibromid in CH3OH bei Anwesenheit von Reinecke‐Salz entstehen [(C6H11)3POCH3] [Cr(SCN)4(NH3)2] und (C6H11)3P(OCH3)2 · H[Cr(SCN)4(NH3)2].Beim Umkristallisieren des Tricyclohexylphosphindijodides aus C2H5OH in Gegenwart von Sauerstoff entsteht [(C6H11)3PO]2 · HJ3.

  DOI：

  10.1002/zaac.19562880309

文献信息

• The reaction of diiodotriorganophosphorus compounds with dicobalt octacarbonyl; isolation of a new isomeric form of [R3PI] [CoI3(PR3)]
  作者：Helen P. Lane、Stephen M. Godfrey、Charles A. McAuliffe

  DOI：10.1016/0020-1693(95)04813-8

  日期：1996.6

  The novel reaction of R3PI compounds with dicobalt octacarbonyl has been investigated and compared to previous studies involving the reaction of R3PI2 compounds with cobalt metal powders. The products produced from both reactions have identical stoichiometries but, surprisingly, possess different structures. Infrared and Raman spectroscopic studies and X-ray powder diffraction clearly show that the

  R的新颖反应3与八羰基二钴PI化合物进行了研究，并与涉及R的反应以前的研究3 PI 2种化合物与钴金属粉末。由两个反应产生的产物具有相同的化学计量，但是令人惊讶地具有不同的结构。红外和拉曼光谱研究以及X射线粉末衍射清楚地表明，由R 3 PI 2与Co 2（CO）8反应得到的产物是[R 3 PI] [CoI 3（PR 3）]的新异构形式。]，与从R 3反应中分离出的产物相比PI 2与钴金属粉末。报告了[R 3 PI] [CoI 3（PR 3）]的这种新异构形式的七个实例，并已通过元素分析，拉曼光谱和定量电子光谱以及磁数据进行了表征，后者表明发生了一些反铁磁耦合。报告和讨论了对这些反应的反应机理的一些一般研究。
• The X-ray crystal structure of [Zn(PEt3)I2]2, the first 1:1 zinc(II) complex of a tertiary phosphine of low steric requirements, prepared by the reaction of unactivated zinc metal with diiodotriethylphosphorane
  作者：Neil Bricklebank、Stephen M. Godfrey、Charles A. McAuliffe、Anthony G. Mackie、Robin G. Pritchard

  DOI：10.1039/c39920000944

  日期：——

  Unactivated zinc powder reacts with R3Pl2(RMe, Et, Prn, Bun) to yield the unexpected 1 : 1 adducts of zinc(II), Zn(R3P)I2; the X-ray crystal structure of triethylphosphine complex shows it to be dimeric [Zn(PEt3)l2]2.

  未活化的锌粉与 R3Pl2（RMe、Et、Prn、Bun）发生反应，生成了意想不到的 1 : 1 的锌（II）加合物 Zn(R3P)I2；三乙基膦配合物的 X 射线晶体结构显示它是二聚体 [Zn(PEt3)l2]2。
• Inorganic Grignard analogues. Reaction of cobalt powder with triorganodiiodophosphorus compounds to form [PR3I][Co(PR3)I3]. Crystal structure of [PPh3I][Co(PPh3)I3], and isolation of the novel complexes [PPh3I][Co(PPh3)IBr2] and [SbPh3I][Co(SbPh3)I3]
  作者：Stephen M. Godfrey、Helen P. Lane、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930001599

  日期：——

  The reactions of a large number of triorganodiiododophosphorus compounds, R3PI2 [R3 = Et3, Pr(n)3, Bu(n)3, PhMe2, Ph2Me, Ph2Pr(n), Ph3 (o-,m- or p-MeC6H4)Ph2, or (m-MeC6H4)3], with unactivated cobalt metal in dry diethyl ether have been studied. All reactions produce the novel ionic complexes [PR3I][Co(PR3)I3] in quantitative yield, illustrated crystallographically for [PPh3I][Co(PPh3)I3]. However, where R3 = PhMe2 both the ionic complex and the cobalt(III) complex [Co(PPhMe2)2I3] are produced from the same reaction. The previously reported isolation of the 'frozen transition-state complex' [Co(PBun3)3I8] from the reaction of Bun3PI2 with cobalt powder has been reinvestigated; when allowed to proceed to completion, the reaction produces the ionic complex described above. The compound Ph3PIBr reacts with cobalt powder to produce the mixed-halide ionic complex [PR3I][Co(PR3)IBr2]. All the complexes [PR3I][Co(PR3)I3] have been studied using Raman and visible spectroscopy, the latter confirming the tetrahedral geometry of the cobalt anion. Very little reaction is observed with the corresponding dibromophosphorus compounds, R3PBr2, but in some cases visible spectroscopic studies on the trace of complex formed suggest a tetrahedral cobalt(II) species, perhaps similar to the iodo-complexes described above. Additionally, Ph3SbI2 reacts with cobalt metal in an analogous way to Ph3PI2 to produce the novel complex [SbPh3I][Co(SbPh3)I3].
• The reaction of bromo- and iodo-phosphoranes with unactivated coarse grain manganese metal powder to yield [MnI₂(phosphine)₂] and [{MnX₂(phosphine)}_n](X = Br or I) by insertion of Mn into the P–X bond. The crystal structure of [MnI₂(PPh₃)₂]
  作者：Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930000371

  日期：——

  The novel reaction of crude manganese metal powder with dibromo- and diiodo-phosphoranes, R3PX2, has been studied. Reaction of the phosphoranes R3PI2 (R = phenyl or substituted aryl) with manganese allows insertion of the metal into P-X bonds and gives the monomeric tetrahedral complexes [MnI2(PR3)2] and MnI2. However, reaction of R3PX2 (R3 = mixed aryl/alkyl, trialkyl; X = Br or I) with manganese, whilst once again proceeding via insertion into P-X bonds, now leads to the quantitative isolation of the polymeric complexes [MnX2(PR3)}n], thus illustrating the subtle nature of these reactions. Examples of both types of complex have been crystallographically characterised and represent rare examples of such. There is some evidence that where R3 = Ph2Me an equilibrium exists and both types of complex, [MnI2(PPh2Me)2] and [MnI2(PPh2Me)}n] can be detected from the same reaction.
• Zur Konstitution und Solvolyse von terti�ren Phosphindihalogeniden ? R3PX2 ?
  作者：K. Issleib、W. Seidel

  DOI：10.1002/zaac.19562880309

  日期：1956.12

  AbstractElementares Chlor, Brom und Jod reagieren unter geeigneten Bedingungen mit aliphatischen, hydroaromatischen und aromatischen tertiären Phosphinen im Mol‐Verh. 1:1. Die Additionsverbindungen sind mit Ausnahme des (C6H11)3PJ2 und (C6H5)3PJ2 äußerst feuchtigkeitsempfindlich. Auf Grund ihres salzartigen Verhaltens können sie als Phosphoniumsalze aufgefaßt werden.Die Phosphindihalogenide setzen sich mit SbCl5, SbBr3 und HgJ2 im Sinne einer Halogen‐Donator‐Akzeptor‐Reaktion um. Die dabei entstehenden Phosphoniumsalze zeigen die Leitfähigkeiten binärer Elektrolyte. Sie enthalten das Phosphoniumkation [R3PX]+. Während Phosphindichloride und Phosphindibromide in Lösung mehr als Neutralmolekeln vorliegen, wird für Phosphindijodide in Lösung eine Dissoziation in [R3PJ]+ und J−‐Ionen bewiesen.Aus Phosphindihalogeniden und Reinecke‐Salz können in wäßrigem Alkohol Phosphinoxyd‐Reinecke‐Säure‐Additionsverbindungen im Verhältnis 1:1, 2:1 und 4:1 dargestellt werden. Bei der Solvolyse von Tricyclohexylphosphindibromid in CH3OH bei Anwesenheit von Reinecke‐Salz entstehen [(C6H11)3POCH3] [Cr(SCN)4(NH3)2] und (C6H11)3P(OCH3)2 · H[Cr(SCN)4(NH3)2].Beim Umkristallisieren des Tricyclohexylphosphindijodides aus C2H5OH in Gegenwart von Sauerstoff entsteht [(C6H11)3PO]2 · HJ3.