1,5-cyclooctadienebis(tetrahydrofuran)rhodium(I) tetrafluoroborate | 120348-64-3

• 英文名称: 1,5-cyclooctadienebis(tetrahydrofuran)rhodium(I) tetrafluoroborate
• 英文别名: [(COD)Rh(THF)2]BF4；[Rh(COD)(THF)2]BF4；rhodium(I)(COD)(THF)2BF4；[Rh(1,5-cyclooctadiene)(THF)2]BF4；[Rh(1,5-cyclooctadiene)(tetrahydrofuran)2]BF4；[Rh(THF)2(COD)][BF4]
• CAS: 120348-64-3
• 化学式: BF₄*C₁₆H₂₈O₂Rh
• 分子量: 442.107
• InChiKey: BHFDQMFVXSGLAX-SUESZSCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 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：

  1,5-cyclooctadienebis(tetrahydrofuran)rhodium(I) tetrafluoroborate 、 (R)-4-苯基-2-(吡啶-2-基)-4,5-二氢恶唑 以 四氢呋喃 为溶剂， 以95%的产率得到[Rh(I)-PyOx-COD](1+)[BF4](1-)
  参考文献：
  名称：

  New chiral oxazoline based-rhodium(I) catalysts: Synthesis, characterisation, heterogeneisation and applications

  摘要：

  New chiral oxazoline-based rhodium(l) homogeneous and heterogeneous catalysts have been prepared and fully characterised through H-1 and C-13 NMR, CP-MAS NMR and XPS. The method used for anchoring the catalyst onto silica was found particularly suitable, since the organometallic complexes remained unchanged over the procedure. The catalysts exhibited a moderate activity and enantioselectivity in hydrogenation of C=O and C=C double bond. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.10.016
• 作为产物：
  描述：

  四氢呋喃 、 silver tetrafluoroborate 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 生成 1,5-cyclooctadienebis(tetrahydrofuran)rhodium(I) tetrafluoroborate
  参考文献：
  名称：

  膦酸酯介导的铑/联吡啶加氢催化剂的固定化

  摘要：

  膦酸酯衍生的2,2'-联吡啶（bpy）配体L的RhL 2复合物固定在原位生成的氧化钛颗粒上。根据Bipy配体的结构-膦酸酯端基所连接的系链（1或2）的数量及其在2,2'-联吡啶骨架（4,4'-，5,5'-，或6,6'-位）-生成的负载型催化剂表现出可比的化学选择性，但在氢气压力下加氢6-甲基-5-庚基-2-酮的动力学不同。六种负载型催化剂的表征表明，每种膦酸酯衍生的2,2'-联吡啶的内在几何形状导致具有不同微观结构和不同RhL 2排列的负载型催化剂 固体表面的有机物种类，从而影响它们的反应性。

  DOI：

  10.1002/chem.201705283
• 作为试剂：
  描述：

  苯乙烯 在 1,5-cyclooctadienebis(tetrahydrofuran)rhodium(I) tetrafluoroborate 、 1-(12,14-Dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yl)pyrrolo[2,3-b]pyridine 、 频那醇硼烷 、 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 苏合香醇 、 苯乙醇
  参考文献：
  名称：

  Exploring the utility of a new chiral phosphoramidite P,N-ligand derived from (R)-BINOL and 7-azaindole in asymmetric catalysis

  摘要：

  对 7-氮杂吲哚进行锂化，然后用[(R)-(1,1′-萘-2,2′-二基)]亚磷酸氯化物淬灭，得到了新的手性磷酰胺 1，分离收率为 92%。将 0.5 等量的[(COD)MCl]2（M = Rh、Ir；COD = η4-1,5-环辛二烯）与 2 等量的 1 处理，可得到相应的[(COD)MCl]2。用 1 的 1 个等量物处理(PPh3)3RhCl，得到的[(PPh3)(κ2-P,N-1)RhCl](3)为分析纯固体，分离收率为 74%。在研究 1 与 0.5 等量的[(COD)RhCl]2 和 1 等量的 AgBF4 的混合物反应时，生成了[(κ2-P,N-1)2Rh]+BF4-（4a）和[(COD)(κ2-P,N-1)Rh]+BF4-（5a）的不可分离混合物。在使用 [(COD)IrCl]2 的类似条件下，得到了[(COD)(κ2-P,N-1)Ir]+BF4- (5b) 复合物，分离收率为 86%。用 1 处理 0.5 等量的 [(η3-烯丙基)PdCl]2，可得到 [(η3-烯丙基)(κ2-P,N-1)Pd]+Cl-（6），分离收率为 86%。研究了 1 在铂族金属介导的不对称化学转化中的应用，包括烯烃氢化和氢硼化、酮氢硅化和烯丙基烷基化。

  DOI：

  10.1139/v08-092

文献信息

• Rhodium bis-phosphine catalysts on mesoporous silica supports: new highly efficient catalysts for the hydrogenation of alkenes
  作者：Cathleen M. Crudden、Daryl Allen、Michael D. Mikoluk、Jian Sun

  DOI：10.1039/b102355c

  日期：——

  A bidentate rhodium phosphine complex anchored onto a mesoporous molecular sieve was shown to be an active catalyst for the hydrogenation of alkenes, with the activity dependent on the method of grafting, and in general, exceeding that of related homogeneous catalysts.

  锚定在介孔分子筛上的二齿铑膦配合物被证明是烯烃加氢的活性催化剂，其活性取决于接枝方法，通常超过相关的均相催化剂。
• Hydrodefluorination of Fluorobenzene and 1,2-Difluorobenzene under Mild Conditions over Rhodium Pyridylphosphine and Bipyridyl Complexes Tethered on a Silica-Supported Palladium Catalyst
  作者：Hong Yang、Hanrong Gao、Robert J. Angelici

  DOI：10.1021/om990151e

  日期：1999.6.1

  Fluorobenzene and 1,2-difluorobenzene are defluorinated under very mild conditions by H2 (4 atm) at 70 °C in the presence of NaOAc. The heterogeneous catalysts for these reactions contain the rhodium pyridylphosphine (1) and bipyridyl (2) complexes [Rh(COD)(1)]BF4 and [Rh(COD)(2)]BF4 tethered to heterogeneous Pd−SiO2.

  氟苯和1,2-二氟苯在非常温和的条件下，在NaOAc的存在下，在70°C下，通过H 2（4 atm）进行脱氟。用于这些反应的非均相催化剂包含吡啶鎓吡啶膦（1）和联吡啶（2）络合物[Rh（COD）（1）] BF 4和[Rh（COD）（2）] BF 4束缚到非均相Pd-SiO 2。
• Study of the Bonding Properties of the New Ligands C₅H₃N(2-R‘)(6-CH₂PPhR) toward Rhodium(I). Evidence for a Dynamic Competition for Bonding between O- and N-Donor Centers When R = <i>o</i>-Anisyl, R‘ = Me
  作者：Hong Yang、Noël Lugan、René Mathieu

  DOI：10.1021/om960982+

  日期：1997.5.1

  The bonding properties of the optically active chiral-at-P polydentate ligands C5H3N(2-R')(6-CH2PPhR) (R = Me, R' = H, Me; R o-anisyl, R' = H, Me) and the achiral ligand C5H3N(2-Me)(6-CH2PPh2) toward (COD)Rh+ are reported. The results show that steric hindrance of the 2-position of the pyridyl ring induces a labile character of the Rh-N bond. Moreover, for R = o-anisyl and R' = Me, a dynamic competition for bonding between the N-and O-donating centers is observed. Comparison of the solid state structures of complexes [Rh(COD)(C5H4N(2-CH2PPhMe)][BF4] and [Rh(COD)(C5H3N(2-Me)(6-CH2PPh2)][BF4] shows a significant bond lengthening of the Rh-N bond in the latter complex, consistent with its fluxional behavior observed in solution.
• Complexing and catalytic properties of easily available chiral iminophosphite based on biphenyl-2,2"-diol
  作者：V. N. Tsarev、A. A. Kabro、S. K. Moiseev、V. N. Kalinin、O. G. Bondarev、V. A. Davankov、K. N. Gavrilov

  DOI：10.1023/b:rucb.0000037848.27038.f8

  日期：2004.4

  A chiral iminophosphite ligand based on biphenyl-2,2'-diol and its chelates with rhodium(I) and palladium(II) were synthesized for the first time. Successful use of these compounds in asymmetric allylic substitution was demonstrated. The enantioselectivity of palladium-catalyzed alkylation of methyl pent-3-en-2-yl carbonate with dimethyl malonate reached 70%, that in the alkylation of 1,3-diphenylallyl acetate with dimethyl malonate was 88%. In the rhodium-catalyzed sulfonylation of 1,3-diphenylallyl acetate with sodium p-toluenesulfinite, the enantioselectivity was 56%.
• Iminoarylphosphites with ferrocenylidene and cymantrenylidene fragments: Coordination properties and use in palladium-catalysed asymmetric allylic substitution
  作者：K.N. Gavrilov、V.N. Tsarev、M.G. Maksimova、O.G. Bondarev、E.A. Rastorguev、S.E. Lyubimov、P.V. Petrovskii、V.A. Davankov

  DOI：10.1016/j.molcata.2006.06.025

  日期：2006.11

  Complexation of the chiral P,N-bidentate ferrocene- and cymantrene-based iminoarylphosphites with [Rh(CO)(2)O-12, [Rh(COD)(THF)(2)]BF4, [Pd(allyl)Cl](2), [Pt(allyl)Cl](4), [Pd(COD)Cl-2] and [Pt(COD)Cl-2] was found to give chelate complexes [Rh(CO)(eta(2)-PN)Cl], [Rh(COD)(eta(2)-PN)]BF4, [M(allyl)(eta(2)-PN)]BF4 (M = Pd, Pt) and cis-[M(eta(2)-PN)Cl-2)] (M = Pd, Pt), correspondingly. With the new P,N-ligands, up to 97% ee was achieved in the asymmetric Pd-catalysed alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. In the enantioselective amination of 1,3-diphenyl-2-propenyl acetate with sodium diformylamide, up to 96% enantioselectivity was achieved. (c) 2006 Elsevier B.V. All rights reserved.