fluorocarbonylbis(triphenylphosphine)rhodium(I) | 58167-05-8

• 英文名称: fluorocarbonylbis(triphenylphosphine)rhodium(I)
• 英文别名: carbonyl{bis(triphenylphosphine)}rhodium(I) fluoride；trans-[Rh(F)(CO)(P(Ph)₃)₂]；trans-[(triphenylphosphine)2Rh(CO)F]；trans-[(Ph3P)2RhF(CO)]；trans-[RhF(CO)(PPh3)2]
• CAS: 58167-05-8；22481-17-0
• 化学式: C₃₇H₃₀FOP₂Rh
• 分子量: 674.496
• InChiKey: SKPKXFIYRGZRGI-UHFFFAOYSA-M

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：

  fluorocarbonylbis(triphenylphosphine)rhodium(I) 在 PPh₃ 作用下， 以 乙腈 为溶剂， 生成 trans-carbonyl(thionitro)bis(triphenylphosphine)rhodium(I)
  参考文献：
  名称：

  Coordination chemistry of NSO−, NSO2− and S3N− ligands: comparison of electronic structure of RhNSO, RhSH and RhCl complexes

  摘要：

  CsNSO2 reacts with fluoro complexes, trans-[M(CO)F(PPh3)2] (M = Rh, Ir) to give sulfonylnitrido complexes, trans-[M(CO)(NSO2)(PPh3)2] which react with triphenylphosphine to afford thionitro complexes, trans-[M(CO)(NSO)(PPh3)2]. The thionitro complexes are also prepared by the reaction of CsNSO2 with hydrido complexes, [MH(CO)(PPh3)3]. Reaction of CsNSO2 with [RuH2(CO)(PPh3)2] yields [Ru(CO)(NSO2)2(PPh3)2]. The sulfonylnitrido complexes of the type Cs2[M'(NS)(NSO2)2Cl3] (M' = Ru, Os) are prepared by the reaction of CsNSO2 and [M'(NS)Cl3]. The reactions of heptasulfurimide with [RhCl(PPh3)3] and [Rh(CO)Cl(PPh3)2] afford disulfidothinitrato complexes [Rh(S3N)(PPh3)2] and [Rh(CO)(S3N)(PPh3)2], respectively. CNDO/2 molecular orbital calculations have been performed on the model systems trans-[Rh(CO)L(PH3)2] (L = NSO, SH, Cl) in order to investigate the nature and energetics of the interaction between rhodium and NSO, SH, Cl ligands. The computed trends for Rh-X, Rh-C and C-O bond strengths, as measured by Wiberg indices and charge distributions, suggest that the strength of the coordination bond Rh-L increases in the order [Rh-NSO] < [Rh-Cl] < [Rh-SH] and the strength of the Rh-C bond increases in the order [Rh(CO)Cl(PH3)2] < [Rh(CO)(NSO)-(PH3)2] < [Rh(CO)(SH)(PH3)2]. The trend in C-O bond strength is [Rh(CO)Cl(PH3)2] > [Rh(CO)(NSO)-(PH3)2] > [Rh(CO)(SH)(PH3)2]. The NSO group is the worst pi-acceptor amongst the three ligands.

  DOI：

  10.1016/s0020-1693(00)90151-8
• 作为产物：
  描述：

  FRh(C₂F₄)(P(C₆H₅)3)2 在 CO 作用下， 以 二氯甲烷 为溶剂， 以>90的产率得到fluorocarbonylbis(triphenylphosphine)rhodium(I)
  参考文献：
  名称：

  氟有机金属化学：古巴簇[FRh（C2H4）（C2F4）] 4的合成，结构和化学

  摘要：

  DOI：

  10.1021/om00148a016

文献信息

• Migration of a hydride ligand to a difluorocarbene ligand bound to rhodium. The synthesis and crystal structure of RhCl2(CF2H)(PPh3)2
  作者：A.K. Burrell、G.R. Clark、J.G. Jeffrey、C.E.F. Rickard、W.R. Roper

  DOI：10.1016/0022-328x(90)85384-b

  日期：1990.5

  RhCl2(CF2H)(CO)(PPh3)2. A study of this reaction, by multinuclear NMR spectroscopy and 2H-labelling experiments led to the proposal of a mechanism for the formation of RhCl2(CF2H)(CO)(PPh3)2 that involves hydride migration to a cationic difluorocarbene ligand bound to rhodium. Another difluoromethyl complex RhCl2(CF2H)(PPh3)2 is formed when RhHCl2(PPh3)3 is treated with Hg(CF3)2. The crystal structure

  的Rh（CF 3）（CO）（PPH 3）2已经通过处理RhH的（CO）（PPH制成3）3与汞（CF 3）2，并发现其显示反应性与16e的一致- ，d 8复杂，因为它经历了许多小分子的添加，包括O 2，X 2（X = Cl，Br，I）和MeI。Rh（CF 3）（CO）（PPh 3）2的处理用含水酸处理的三氟甲基导致三氟甲基水解为羰基配体。证实该反应是通过二氟卡宾中间体进行的，来自与干燥的HCl的反应，得到了RhCl 2（CF 2 H）（CO）（PPh 3）2。通过多核NMR光谱和2 H标记实验对该反应的研究导致提出了形成RhCl 2（CF 2 H）（CO）（PPh 3）2的机制，该机制涉及氢化物向阳离子二氟卡宾的迁移。配体与铑结合。另一种二氟甲基络合物RhCl 2（CF 2 H）（PPh 3）2时RhHCl形成2（PPH 3）3与汞（CF处理3）2。该配合物的晶体结构已经确定，并且显示出方形的金字塔形几何结构，其中CF
• Rhodium and iridium complexes with thiolate and tertiary phosphine ligands. The synthesis and structures of trans-[Ir(SC₆H₃Cl₂-2,6)(CO)(PPh₃)₂], [Rh₂(μ-SC₆H₃Prⁱ₃-2,4,6)₂(CO)₂(PPh₃)₂], [Rh₂H₂(μ-SC₆H₄PPh₂-2)₂(CO)₂(PPh₃)₂][BF₄]₂, and [Rh₂I₆(MeSC₆H₄PPh₂-2)₂]
  作者：Jonathan R. Dilworth、David Morales、Yifan Zheng

  DOI：10.1039/b005588n

  日期：——

  Reaction of [MF(CO)(PPh3)2] (M = Rh or Ir) with bulky aromatic thiols ArSH gave the binuclear complexes [M2(μ-SAr)2(CO)2(PPh3)2] (M = Rh, SAr = SC6H2Pri3-2,4,6 or SC6H3Me2-2,6) and mononuclear complexes [M(SAr)(CO)(PPh3)2] (M = Rh or Ir, SAr = SC6H3Cl2-2,6 or SC6H4SiPh3-2; M = Ir, SAr = SC6H2Pri3-2,4,6 or SC6H3Me2-2,6. The crystal structure of [Rh2(μ-SC6H3Pri3-2,4,6)2(CO)2(PPh3)2] showed a binuclear

  [MF（CO）（PPh 3）2 ]（M = Rh或Ir）与大量芳烃的反应硫醇ArSH给出了双核络合物[M 2（μ-SAr）2（CO）2（PPh 3）2 ]（M = Rh，SAr = SC 6 H 2 Pr i 3 -2,4,6或SC 6 H 3 Me 2 -2,6）和单核配合物[M（SAR）（CO）（PPH 3）2 ]（M =铑或铱，SAR = SC 6 H ^ 3氯2 -2,6或SC 6 H ^ 4 SIPH 3 - 2; M = Ir，SAr = SC 6 H 2 Pr i 3 -2,4,6或SC6 H 3 Me 2 -2,6。的晶体结构的[Rh 2（μ-SC 6 H ^ 3镨我3 -2,4,6-） 2（CO） 2（PPH 3） 2 ]表明的双核硫醇盐桥芯而物[Ir（SC的6 ħ 3 Cl 2 -2,6）（CO）（PPh 3） 2 ]揭示了具有反式PPh 3的常规正方形平面几何形状 配体。三种铑配合物被证明是有效的催化剂
• The nature of the bridging nitrido ligand. Synthesis and reactivity of heterobimetallic nitrido-bridged compounds
  作者：Carolyn M. Jones、Nancy M. Doherty

  DOI：10.1016/0277-5387(94)00355-i

  日期：1995.1

  )(OSiMe 3 ) 3 and a group VIII metal chloride or hydride product. Comparison of the reactivity and spectroscopic data among the nitrido-bridged compounds and with related iridium(I) and rhodium(I) complexes suggests that the nitrido-bridged compounds are best viewed as adducts in which anionic [(R 3 SiO) 3 VN:] − acts as a simple two-electron donor to the 14-electron cationic [M(L)(PPh) 2 ] + fragment

  摘要异双金属亚硝基桥接化合物（R 3 SiO）3VNM（CO）（PPh 3）2（RMe或Et和MIr或Rh）和（Me 3 SiO）3VNRh （PPh 3）3是通过钒硅烷基酰亚胺化合物V（NSiR 3）（OSiR 3）3和VIII族金属氟化物MF（L）（PPh 3）2的缩合反应合成的。小分子（MeI，O 2，H 2）氧化成（R 3 SiO）3VNIr（CO）（PPh 3）2的铱（I），产生铱（III）化合物，其中VNIr相互作用得以保留。然而，相比之下，（Me 3 SiO）3VNM（L）（PPh 3）2中的亚硝基键很容易被甲硅烷基化试剂（ClSiMe 3，ClSiEt 3，HSiEt 3）裂解，生成V（NSiR 3 ）（OSiMe 3）3和第VIII族金属氯化物或氢化物产物。
• Selective Formation and Characterization of a Rh^III Difluorido λ⁴ -Trifluorosulfanyl Complex
  作者：Nils Pfister、Thomas Braun、Philipp Wittwer、Mike Ahrens

  DOI：10.1002/zaac.201800323

  日期：2018.9.17

  A general route to access the Vaska type fluorido complexes trans‐[Rh(F)(CO)(PR3)2] [R = Et (6), Ph (7), iPr (8), Cy (9), tBu (10)] was developed by treatment of trans‐[Rh(Cl)(CO)(PR3)2] (1–5) with Me4NF. The molecular structures of 8 and 9 were determined by X‐ray crystallography. Treatment of the complex 6 with SF4 resulted in the selective formation of complex cis,trans‐[Rh(F)2(SF3)(CO)(PEt3)2] (11)

  访问Vaska型氟络合物反式-[Rh（F）（CO）（P R 3）2 ]的一般路线[ R = Et（6），Ph（7），i Pr（8），Cy（9） ，t Bu（10）]是通过用Me 4 NF处理反式[Rh（Cl）（CO）（PR 3）2 ]（1 – 5）而开发的。通过X射线晶体学确定8和9的分子结构。综合体的治疗6SF 4导致选择性形成顺式，反式-[Rh（F）2（SF 3）（CO）（PEt 3）2 ]（11），而其他氟化物不发生反应。
• Synthesis of neutral iridium(III) and rhodium(III) complexes with the proligands Pri2P(C6H4SH-2) [priPSH]; PhP(C6H4SH-2)2 [phPS2H2] and PhP(C2H4SH)2 [ePS2H2]. The X-ray crystal structures of [Ir(priPS)3] and [Rh(H)(phPS2)(CO)(PPh3)]
  作者：David Morales-Morales、Sergio Rodrı́guez-Morales、Jonathan R. Dilworth、Antonio Sousa-Pedrares、Yifan Zheng

  DOI：10.1016/s0020-1693(02)00695-3

  日期：2002.4

  with iridium and rhodium precursors has been explored. By reacting IrCl3 with priPSH in the presence of NEt3 as base, the octahedral Ir(III) specie [Ir(priPS)3] was obtained and its crystal structure determined. Reactions of the potentially tridentated proligands phPS2H2 and ePS2H2 with trans-[MF(CO)(PPh3)2] (M=Rh and Ir) were also investigated. Complexes of general formula [M(H)(phPS2)(CO)(PPh3)] were

  摘要研究了杂磷-硫配体priPSH，phPS2H2和ePS2H2与铱和铑前体的反应性。在NEt3作为碱的存在下，通过使IrCl3与priPSH反应，获得八面体Ir（III）物种[Ir（priPS）3]，并确定了其晶体结构。还研究了潜在的三齿配体phPS2H2和ePS2H2与反式[MF（CO）（PPh3）2]（M = Rh和Ir）的反应。与phPS2H2得到通式[M（H）（phPS2）（CO）（PPh3）]的配合物。[Rh（H）（phPS2）（CO）（PPh3）]的单晶X射线结构测定表明该络合物为八面体。与脂族配体ePS2H2的反应提供了与具有phPS2H2的类似的物质。