[(η(5)-C5H5)(CO)2Ru(P(OC6H4NMe)(OC6H4NHMe))]BF4 | 240122-99-0

• 英文名称: [(η(5)-C5H5)(CO)2Ru(P(OC6H4NMe)(OC6H4NHMe))]BF4
• 英文别名: [(CO)2Ru(C5H5)(P(OC6H4NMe)(OC6H4NHMe))]BF4
• CAS: 240122-99-0
• 化学式: BF₄*C₂₁H₂₀N₂O₄PRu
• 分子量: 583.249
• InChiKey: ZJESWINVYXMVCU-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：

  [(η(5)-C5H5)(CO)2Ru(P(OC6H4NMe)(OC6H4NHMe))]BF4 在 base 作用下， 以 四氢呋喃 为溶剂， 生成 (CO)2Ru(C5H5)(P(OC6H4NMe)2)
  参考文献：
  名称：

  Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

  摘要：

  Ruthenium phosphorane complexes, Cp(CO)(2)Ru{P(OC(6)H(4)Z)(2)} (Z = NMe, O), react with lithium diisopropylamide (LDA) to give Li[{eta(5)-C5H4P(OC(6)H(4)Z)(2)}(CO)(2)RU] (5) In this reaction, one of the protons on the Cp ring is abstracted by LDA and then migration of the phosphorane fragment to the Cp ring takes place. Treatment of 5 with RX (CH3I, PhCH2Cl, Ph3SnCl, HOCOCF3, CD3I) yields {eta(5)-C5H4P(OC(6)H(4)Z)(2)}(CO)(2)RuR (2). The structure of one of the products, {eta(5)-C5H4P(OC6H4NMe)(2)}(CO)(2)RuCH2Ph, was determined by X-ray analysis. A reaction of a cationic phosphite complex, [Cp(CO)(2)Ru{P(OC6H4NMe)(OC6H4NMeH)}]BF4 (6), with 2 equiv of LDA also gives 5. However, the following addition of RX at -30 degrees C gives the unexpected phosphorane-migration complex {eta(5)-C5H4P(OC6H4NMe)(2)}(CO)(2)RuR, which contains one O atom and one N atom in apical positions and in equatorial positions as well. The complex gradually isomerizes to a thermally more stable apical oxygen-equatorial nitrogen isomer (2).

  DOI：

  10.1021/om9904145
• 作为产物：
  描述：

  (CO)2Ru(C5H5)(P(OC6H4NMe)2) 在 acid 作用下， 以 四氢呋喃 为溶剂， 生成 [(η(5)-C5H5)(CO)2Ru(P(OC6H4NMe)(OC6H4NHMe))]BF4
  参考文献：
  名称：

  Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

  摘要：

  Ruthenium phosphorane complexes, Cp(CO)(2)Ru{P(OC(6)H(4)Z)(2)} (Z = NMe, O), react with lithium diisopropylamide (LDA) to give Li[{eta(5)-C5H4P(OC(6)H(4)Z)(2)}(CO)(2)RU] (5) In this reaction, one of the protons on the Cp ring is abstracted by LDA and then migration of the phosphorane fragment to the Cp ring takes place. Treatment of 5 with RX (CH3I, PhCH2Cl, Ph3SnCl, HOCOCF3, CD3I) yields {eta(5)-C5H4P(OC(6)H(4)Z)(2)}(CO)(2)RuR (2). The structure of one of the products, {eta(5)-C5H4P(OC6H4NMe)(2)}(CO)(2)RuCH2Ph, was determined by X-ray analysis. A reaction of a cationic phosphite complex, [Cp(CO)(2)Ru{P(OC6H4NMe)(OC6H4NMeH)}]BF4 (6), with 2 equiv of LDA also gives 5. However, the following addition of RX at -30 degrees C gives the unexpected phosphorane-migration complex {eta(5)-C5H4P(OC6H4NMe)(2)}(CO)(2)RuR, which contains one O atom and one N atom in apical positions and in equatorial positions as well. The complex gradually isomerizes to a thermally more stable apical oxygen-equatorial nitrogen isomer (2).

  DOI：

  10.1021/om9904145

文献信息

• Syntheses, Structures, and Berry Pseudorotation of Ruthenium−Phosphorane Complexes
  作者：Hiroshi Nakazawa、Kazumori Kawamura、Kazuyuki Kubo、Katsuhiko Miyoshi

  DOI：10.1021/om990044k

  日期：1999.8.1

  During the course of preparation of 2b, a phosphite complex (3) was isolated, which reacted with a Lewis base to give 2b. The X-ray structures of 2b, 4b, and 3 were determined. 2b and 4b have slightly distorted trigonal-bipyramidal geometries. From the variable-temperature 31P NMR study for 4c, the activation parameters for Berry pseudorotation around the pentacoordinate phosphorus were determined to

  含有高价磷配位体的钌配合物，（E = NH（图2a），NME（图2b），或O（4A））， （4B），及（4C），分别在[Cp的（CO）的反应来制备2的Ru P（OPh）3 }] BF 4（1）与相应的芳基醇或芳基胺和Et 3 N或n -BuLi。的光谱数据的比较（M = RU，Fe）的（E = NH，NME，O）揭示了在Ru-P键合更极化为M δ + -P δ -比Fe-P键。在制备2b的过程中，分离了亚磷酸酯配合物（3），使其与路易斯碱反应生成2b。确定了2b，4b和3的X射线结构。2b和4b的三角形-双锥体几何形状略有变形。从可变温度31为P NMR研究图4c，被确定为Δ周围的五配位磷浆果pseudorotation激活参数ħ ⧧ = 42.1±0.5千焦耳摩尔- 1，Δ小号⧧= -91.1±1.6Ĵ摩尔- 1 ķ - 1，和Δ ģ 340 ⧧ = 73.1±0.7千焦耳摩尔- 1。