(μ-η(5):η(5)-1,3,4-triphospha-2,5-di-tert-butylcyclopentadienyl)bis[(η(5)-pentamethylcyclopentadienyl)ruthenium] hexafluorophosphate | 169063-32-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (μ-η(5):η(5)-1,3,4-triphospha-2,5-di-tert-butylcyclopentadienyl)bis[(η(5)-pentamethylcyclopentadienyl)ruthenium] hexafluorophosphate
• CAS: 169063-32-5
• 化学式: C₃₀H₄₈P₃Ru₂*F₆P
• 分子量: 848.737
• InChiKey: GCWUIWYLYDCOAR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.01
• 重原子数：
  42
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  (cyclopentadienyliron)(1,3,4-triphospha-2,5-di-tert-butylcyclopentadienyl)(pentamethylcyclopentadienyl)bis(acetonitrile)rutheniumhexafluorophosphate 以 硝基甲烷 为溶剂， 生成 (μ-η(5):η(5)-1,3,4-triphospha-2,5-di-tert-butylcyclopentadienyl)bis[(η(5)-pentamethylcyclopentadienyl)ruthenium] hexafluorophosphate
  参考文献：
  名称：

  Syntheses and Structures of Diruthenium Triple-Decker Complexes with Bridging 1,2,4-Triphospholyl and 1-Arsa-3,4-Diphospholyl Anions

  摘要：

  Yellow-brown oils, characterized spectroscopically as [Cp*Ru(eta(5)-C-2-t-Bu(2)P(3))], 11, and [Cp*Ru(eta(5)-C-2-t-Bu(2)AsP(2))], 12, were isolated from the reaction of [Cp*Ru(CH3CN)(3)][PF6], 6, with [Li(C-2-t-Bu(2)P(3))], 2, or [Li(C-2-t-Bu(2)AsP(2))], 4, respectively. Both 11 and 12 reacted further with 6 to give the triple-decker complexes [Cp*Ru(mu-eta(5):eta(5)-C-2-t-Bu(2)P(3))RuCp*][PF6], 7, and [Cp*Ru(mu-eta(5):eta(5)-C-2-t-Bu(2)AsP(3))RuCp*][PF6], 8, in which the triphospholyl or arsadiphospholyl anions bridge two ruthenium centers. Both 7 and 8 have been characterized by single-crystal X-ray crystal structure determinations. Crystal data for C30H48F6P4Ru2, 7: M = 848.7, P2(1)2(1)2(1), a = 12.642(9) Angstrom, b = 15.151(10 Angstrom, c = 18.176(10) Angstrom, V = 3481.4 Angstrom(3), D-caled = 1.62 g cm(-3) (Z = 4) mu = 10.8 cm(-1) for Mo K alpha radiation (lambda = 0.7107 Angstrom), final R = 0.055, R(w) = 0.057, from 2716 observed reflections (3437 measured). Data for C30H48AsF6P3Ru2, 8: M = 892.7, P2(1)2(1)2(1), a = 12.650(9) Angstrom, b = 15.147(8) Angstrom, c = 18.111(10) Angstrom V = 3470.1 Angstrom(3), D-caled = 1.71. g cm(-3) (Z = 4) mu = 19.9 cm(-1) for Mo K alpha radiation (lambda = 0.7107 Angstrom), final R = 0.049, R(w) = 0.053, from 2760 observed reflections (3430 measured). Attempts to prepare mixed-metal triple-decker complexes by reacting [Fe(eta(5)-C(5)R(5))(eta(5)-C-2-t-Bu(2)P(3))] (R = H, 14a; R = Me, 14b] or [Fe(eta(5)-C(5)R(5))(eta(4)5-C-2-t-Bu(2)AsP(2))] (R = H, 15a; R = Me, 15b) with 6 were unsuccessful. Likewise, when either 14a or 15a is treated with 6 the intermediate complexes [Fe(eta(5)-C5H5)(eta(5)-C-2-t-Bu(2)P(3))RuCp*(CH3CN)(2)][PF6], 17, or [Fe(eta(5)-C5H5)(eta(5)-C-2-t-Bu(2)AsP(2))RuCp*(CH3 CN)(2)][PF6], 18, were isolated and spectroscopically characterized. When these were heated in nitromethane, a ring transfer occurred and the triple-decker species 7 or 8 was observed. Similar reactions involving 14b or 15b led directly to 7 or 8 without detection of any intermediate complexes.

  DOI：

  10.1021/om00009a048

文献信息

• Polyhetero-ferrocenes and -ruthenocenes derived from the 1,4,2-diphosphastibolyl ring anion [P2SbC2But2]−
  作者：Steven J. Black、Matthew D. Francis、Cameron Jones

  DOI：10.1039/a700869d

  日期：——

  The complex [RuCl 2 (PPh 3 ) 3 ] reacted with the 1,4,2-diphosphastibolyl ring anion [P 2 SbC 2 Bu t 2 ] - (containing ca. 25% of the 1,2,4-triphospholyl anion [P 3 C 2 Bu t 2 ] - ) to produce a cocrystallised mixture (crystal structure) of two isomers of [Ru(η 5 -P 2 SbC 2 Bu t 2 ) 2 ] with [Ru(η 5 -P 2 SbC 2 Bu t 2 )(η 5 -P 3 C 2 Bu t 2 )]. Variable-temperature 31 P- 1 H} NMR studies on the mixture show one of the isomers and the last complex to be fluxional at room temperature. It is believed that an interring Sb · · · Sb interaction in the other isomer restricts its fluxionality in solution. The reaction of [P 2 SbC 2 Bu t 2 ] - with FeCl 2 yielded only one isomer of the heteroferrocene complex [Fe(η 5 -P 2 SbC 2 Bu t 2 ) 2 ] which is also non-fluxional in solution and has a similar oxidation potential to that of ferrocene itself. The heteroruthenocene complexes [Ru(η 5 -P 2 SbC 2 Bu t 2 )(η 5 -C 5 R 5 )] (R = H or Me) were prepared by treating [Ru(η 5 -C 5 R 5 )(MeCN) 3 ] [PF 6 ] (R = H or Me) with [P 2 SbC 2 Bu t 2 ] - . The analogous ferrocene complex [Fe(η 5 -P 2 SbC 2 Bu t 2 )(η 5 -C 5 Me 5 )] (crystal structure) was synthesized by treating a 1∶1 mixture of [P 2 SbC 2 Bu t 2 ] - and Li(C 5 Me 5 ) with half an equivalent of FeCl 2 . Treatment of [M(η 5 -P 2 SbC 2 Bu t 2 )(η 5 -C 5 Me 5 )] (M = Ru or Fe) with [W(CO) 5 (thf)] (thf = tetrahydrofuran) formed the secondary co-ordination complexes [M(η 5 -P 2 SbC 2 Bu t 2 )(η 5 -C 5 Me 5 )W(CO) 5 }] (M = Ru or Fe) in which the W(CO) 5 fragment is η 1 ligated to the phosphorus centre adjacent to the ring antimony centre. A diphosphastibolyl-bridged cationic triple-decker complex [(η 5 -C 5 Me 5 )Ru(µ-η 5 : η 5 -P 2 SbC 2 Bu t 2 )Ru(η 5 -C 5 Me 5 )][PF 6 ] was the product of the reaction of [P 2 SbC 2 Bu t 2 ] - with 2 equivalents of [Ru(η 5 -C 5 Me 5 )(MeCN) 3 ] [PF 6 ].

  ](η 5 3C 2Bu 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 17 18 19 与FeCl2反应只产生一种异构体，即[Fe(η5-P2SbC2But2)2](η53C2Bu2345678910111213141516171819171819。 该反应生成的产物为一种具有双铁环的二茂铁配合物，其结构为[Fe(η5-P2SbC2But2)2](η5