di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium | 12092-47-6

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机铑
• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium
• 英文别名: di-μ-chloro-bis(η(4)-cycloocta-1,5-diene)dirhodium(I)；bis(μ-chloro)bis(η4-cycloocta-1,5-diene)dirhodium(I)；di-μ-chlorobis(η(4)-1,5-cyclooctadiene)dirhodium(I)；bis[μ-chloro-(η(4)-1,5-cyclooctadienyl)rhodium(I)]；di-μ-chloro-bis(η(4)-1,5-cyclooctadiene)dirhodium；di-μ-chlorobis(η(4)-cycloocta-1,5-diene)dirhodium；chloro(1,5-cyclooctadiene)rhodium(I) dimer；di-μ-chloridobis[(η²:η²-cycloocta-1,5-diene)rhodium(I)]；bis(μ-chlorido)bis(((1,2,5,6-η)-1,5-cyclooctadiene)rhodium(I))；di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]dirhodium(I)；di-μ-chlorobis[(1,2,5,6-η4)-1,5-cyclooctadiene]dirhodium；di-μ-chlorobis[(1,2,5,6-η)-1,5-cyclooctadiene]dirhodium；di-μ-chloro-bis(η(4)-1,5-cyclooctadiene)dirhodium(I)
• CAS: 12092-47-6
• 化学式: C₁₆H₂₄Cl₂Rh₂
• 分子量: 493.084
• InChiKey: LGARIVPRHUAOKP-MIXQCLKLSA-N

物化性质

• 熔点：
  243 °C (dec.) (lit.)
• 密度：
  1.94[at 20℃]
• 溶解度：
  易溶于可溶于氯仿、二氯甲烷和甲醇。微溶于大多数常见溶剂。
• 暴露限值：
  ACGIH: TWA 0.01 mg/m3; TWA 1 mg/m3NIOSH: IDLH 2 mg/m3; IDLH 100 mg/m3; TWA 0.001 mg/m3; TWA 0.1 mg/m3
• LogP：
  3.16 at 20℃
• 稳定性/保质期：
  在常温常压下稳定，应避免接触酸、水分或潮湿环境。

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

安全信息

• TSCA：
  Yes
• 危险品标志：
  Xi
• 安全说明：
  S26,S37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  28439000
• 危险性防范说明：
  P264,P280,P302+P352,P337+P313,P305+P351+P338,P362+P364,P332+P313
• 危险性描述：
  H315,H319
• 储存条件：
  保存于2-8°C的密闭阴凉干燥处

SDS

Name:	Chloro-(1 5-cyclooctadiene)-rhodium(i) dimer Material Safety Data Sheet
Synonym:	Di-mu.-chlorobis[1,2,5,6-n)-1,5-cyclooctadiene] dirhodiu
CAS:	12092-47-6

Section 1 - Chemical Product MSDS Name:Chloro-(1 5-cyclooctadiene)-rhodium(i) dimer Material Safety Data Sheet
Synonym:Di-mu.-chlorobis[1,2,5,6-n)-1,5-cyclooctadiene] dirhodiu

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
12092-47-6	Chloro-(1,5-cyclooctadiene)-rhodium (I	100	235-157-6

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk or water.
Never give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Clean up spills immediately, observing precautions in the Protective Equipment section. Sweep up or absorb material, then place into a suitable clean, dry, closed container for disposal. Avoid generating dusty conditions. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 12092-47-6: United Kingdom, WEL - TWA: (listed as rhodium): 0.1 mg/m3 TWA (du and fume) United Kingdom, WEL - STEL: (listed as rhodium): 0.3 mg/m3 STEL ( and fume) United States OSHA: 0.1 mg/m3 TWA (listed under Rhodium).0.001 m TWA (as Rh) (listed under Rhodium soluble compounds).
Belgium - TWA: (listed as rhodium soluble compounds): 0.01 mg/m3 (as Rh) France - VME: (listed as rhodium): 1 mg/m3 VME Germany: (listed as rhodium): 1 mg/m3 VME Malaysia: (listed as rhodium soluble compounds): 0.01 mg/m3 TWA ( Rh) Netherlands: (listed as rhodium soluble compounds): 0.001 mg/m3 M (as Rh) Spain: (listed as rhodium soluble compounds): 0.01 mg/m3 VLA-ED ( Rh) Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystalline powder
Color: Yellow-Orange Crystalline Powder
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 243 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C16H24Cl2Rh2
Molecular Weight: 493.08

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, dust generation, strong oxidants.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Hydrogen chloride, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 12092-47-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Chloro-(1,5-cyclooctadiene)-rhodium (I) dimer - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
S 28A After contact with skin, wash immediately with
plenty of water.
S 37 Wear suitable gloves.
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 12092-47-6: 0
Canada
CAS# 12092-47-6 is listed on Canada's NDSL List.
CAS# 12092-47-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 12092-47-6 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途

(1,5-环辛二烯)氯铑(I)二聚体用于合成催化反应中的金属配体，适用于以下反应和过程：

• 与1,3-二烯及活性烃的催化剂作用；
• 制备手性复合物；
• 耦合反应；
• 不对称氢化反应；
• 硼氢化反应。

反应信息

• 作为反应物：
  描述：

  di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 在 P(C₆H₅)3 作用下， 以 氘代四氢呋喃 为溶剂， 生成 Wilkinson's catalyst
  参考文献：
  名称：

  儿茶酚硼烷与威尔金森催化剂的反应：对过渡金属催化的烯烃硼氢化反应的影响

  摘要：

  儿茶酚硼烷 (HBO 2 C 6 H 4 ) 与 RhCl(PPh 3 ) 3 (1) 的反应会根据 B/Rh 比、溶剂和温度产生多种产物。与催化的烯烃硼氢化特别相关的是 HBO 2 C 6 H 4 降解为 B 2 (O 2 C 6 H 4 ) 3 /«BH 3 » 和二氢化物 RhH 2 Cl(PPh 3 ) 3 (3)。3的分子结构，由X射线衍射确定，具有经向膦配体和顺式氢化物

  DOI：

  10.1021/ja00050a015
• 作为产物：
  描述：

  1,5-环辛二烯 在 HCl 作用下， 以 甲醇 、 苯 为溶剂， 生成 di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium
  参考文献：
  名称：

  铑（I）双（吡唑基）苯基甲烷配合物的制备和反应

  摘要：

  配合物[（LL）Rh（C 2 H 4）Cl] x（I），[（LL）（Rh（cod）Cl）2 ]（II），[（MeLL）Rh（C 2 H 4）2 Cl ]（III）和[（梅尔）的Rh（COD）] +氯-（IV）已经通过双（吡唑基）苯基甲烷配体的PhCH（H的反应中制备的2 PZ）2（LL; H 2 PZ =吡唑基）和PhCH（Me 2 pz）2（MeLL; Me 2 pz = 3,5-二甲基吡唑基）和[Rh（C 2 H 4）2 Cl] 2和[Rh（cod）Cl] 2（鳕鱼＝环辛二烯）。与NaBPh复杂IV发生反应4，以形成[（梅尔）的Rh（COD）] + BPH 4 -（V）。III和IV与一氧化碳反应，得到[（MeLL）Rh（CO）2 ] + [Rh（CO）2 Cl 2 ] -（VI）。配合物I和III在甲醇中产生中性溶液，而II和IV分别表现为1：2和1：1电解质。铑（I）中心通常在I，

  DOI：

  10.1016/s0022-328x(00)90026-3
• 作为试剂：
  描述：

  惕格酸 在 di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 、 氢气 、 6-O-(diphenylphosphino)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose 、 三乙胺 作用下， 以 乙醇 、 苯 为溶剂， 反应 24.0h， 生成 (R)-2-甲基丁酸 、 (S)-(+)-2-甲基丁酸
  参考文献：
  名称：

  三价磷化合物糖衍生物的合成及其在均相不对称加氢中的应用

  摘要：

  糖的二苯基膦和二苯基次膦酸盐衍生物，例如甲基 6-脱氧-4-C-(二苯基膦基)-2,3-O-异亚丙基-α-L-吡喃酮苷、甲基 4-O-(二苯基膦基)-2,3-O-异亚丙基-α-L-rhamnopyranoside,methyl 4-C,4-O-(diphenylphosphino)-2,3-O-isopropylidene-α-L-talopyranoside, 6-deoxy-6-C-(diphenylphosphino)-1,2通过反应合成:3,5-二-O-异亚丙基-α-D-呋喃葡萄糖和6-O-(二苯基膦)-1,2:3,4-二-O-异亚丙基-α-D-吡喃半乳糖二苯基膦-二氢双（2-甲氧基乙氧基）铝酸钠（SDMA）和/或二苯基氯化膦-三乙胺与糖衍生物。几种前手性烯烃（α-乙酰氨基肉桂酸、α-乙酰氨基肉桂酸甲酯、α-苯甲酰氨基肉桂酸、衣康酸、和tiglic acid）使用铑（I）催化剂与糖

  DOI：

  10.1246/bcsj.55.2917

文献信息

• Novel chiral phosphine ligands and complexes from amino acid esters
  作者：Alexandra M. Z. Slawin、J. Derek Woollins、Qingzhi Zhang

  DOI：10.1039/b009074n

  日期：——

  N-Diphenylphosphinoamino acid methyl/ethyl esters RCH(NHPPh2)CO2R′ 1a–1e were prepared in high yield from equimolar amounts of amino acid methyl/ethyl ester hydrochloride and chlorodiphenylphosphine. The reaction proceeds with configurational retention. Oxidation of 1a (R = R′ = CH3) with H2O2 or S8 leads to the N-diphenylphosphinoylalanine methyl ester 2a or N-diphenylthiophosphinoylalanine methyl ester 3a. 1a–1e function as monodentate ligands to [PtCl2(cod)], [RhCl(cod)]2 and [AuCl(tht)] to give cis-[PtCl2(1-P)2], [RhCl(cod)(1-P)] and [AuCl(1-P)]. Two equivalents of chlorodiphenylphosphine react with alanine methyl ester hydrochloride in CH2Cl2 to give N,N-bis(diphenylphosphino)alanine methyl ester, bdppal. This is an excellent bidentate ligand, the chelate complexes [MCl2(bdppal-P,P′)] (M = Pd or Pt) being prepared and studied by X-ray analysis. Oxidation at one P atom in bdppal with either H2O2 or S8 gives N-diphenylphosphino-N-diphenylphosphinoylalanine methyl ester, bdppalO, and N-diphenylphosphino-N-diphenylthiophosphinoylalanine methyl ester, bdppalS, respectively. bdppalO is very difficult to isolate but does react in situ with [PdCl2(cod)] to give [PdCl2(bdppalO-O,P)]. bdppalS reacts with [MCl2(cod)] (M = Pd or Pt) giving [MCl2(bdppalS-P,S)]. The dioxidised product N,N-bis(diphenylphosphinoyl)alanine methyl ester, bdppalO2, does not react with [MCl2(cod)] (M = Pd or Pt), whereas N,N-bis(diphenylthiophosphinoyl)alanine methyl ester, bdppalS2, reacts with [PdCl2(cod)] to give [PdCl2(bdppal-S,S′)]. All the compounds are chiral and have been fully characterised by microanalysis, IR, 31P-1H}, 1H NMR, and FAB+ mass spectroscopies, and in several cases structures are confirmed by X-ray analysis. The crystal structures described and those previously determined reveal the configurational retention of the reactions.

  N-二苯基膦氨基酸甲酯/乙酯 RCH(NHPPh2)CO2R' 1a-1e 高产率地由等摩尔量的氨基酸甲酯/乙酯盐酸盐和氯化二苯基膦制备。反应过程中构型保持不变。1a（R = R' = CH3）的氧化采用 H2O2 或 S8，分别得到 N-二苯基膦酰丙氨酸甲酯 2a 或 N-二苯基硫代膦酰丙氨酸甲酯3a。1a-1e 作为单齿配体与[PtCl2(cod)]、[RhCl(cod)]2 和[AuCl(tht)]反应生成顺式-[PtCl2(1-P)2]、[RhCl(cod)(1-P)]和[AuCl(1-P)]。两当量的氯化二苯基膦与丙氨酸甲酯盐酸盐在 CH2Cl2 中反应生成 N,N-双(二苯基膦)丙氨酸甲酯，bdppal。这是一个极佳的双齿配体，螯合物[MCl2(bdppal-P,P')]（M = Pd 或 Pt）已制备并经 X 射线分析研究。bdppal 中的一个 P 原子被 H2O2 或 S8 氧化分别得到 N-二苯基膦-N-二苯基膦酰丙氨酸甲酯 bdppalO 和 N-二苯基膦-N-二苯基硫代膦酰丙氨酸甲酯 bdppalS。bdppalO 极难分离，但能与[PdCl2(cod)]现场反应生成[PdCl2(bdppalO-O,P)]。bdppalS 与[MCl2(cod)]（M = Pd 或 Pt）反应生成[MCl2(bdppalS-P,S)]。过氧化产物 N,N-双(二苯基膦酰)丙氨酸甲酯 bdppalO2 与[MCl2(cod)]（M = Pd 或 Pt）不反应，而 N,N-双(二苯基硫代膦酰)丙氨酸甲酯 bdppalS2 与[PdCl2(cod)]反应生成[PdCl2(bdppal-S,S')]。所有这些化合物都是手性的，并通过元素分析、红外、31P-1H}、1H NMR 和 FAB+质谱等手段进行了全面表征，在数个例子中通过 X 射线分析确认了结构。所述晶体结构及先前所测定的那些晶体结构揭示了反应中的构型保持现象。
• Asymmetric Hydrogenation Using Diphenylphosphinite Derivatives of Carbohydrates as the Chiral Ligand of Rhodium Catalysts
  作者：Mitsuji Yamashita、Manabu Naoi、Hiroyuki Imoto、Tatsuo Oshikawa

  DOI：10.1246/bcsj.62.942

  日期：1989.3

  Diphenylphosphinite derivatives of carbohydrates (L-rhamnose, D-mannitol, and cellulose), which have asymmetric centers on the skeletons were synthesized. Asymmetric hydrogenations of prochiral substrates using rhodium catalysts with the prepared chiral phosphinite ligand were carried out to obtain chiral substances in 8–78% optical yield.

  合成了在骨架上具有不对称中心的碳水化合物（L-鼠李糖、D-甘露糖醇和纤维素）的二苯基次膦酸酯衍生物。使用铑催化剂与制备的手性次膦酸盐配体进行前手性底物的不对称氢化，以8-78%的光学产率获得手性物质。
• Carbene complexes
  作者：Bekir Çetinkaya、Peter B. Hitchcock、Michael F. Lappert、David B. Shaw、Kostas Spyropoulos、Nicholas J.W. Warhurst

  DOI：10.1016/0022-328x(93)86084-u

  日期：1993.10

  yield [LR R and L(su323)R}  (CH2)2]. Complex 2 provides a rare example of a bridging bis(carbene) dimetal complex and the first for one derived from an enetetramine. The X-ray structures of1–5 show that (i) the mutually trans-RhCcarb bonds for 1 and 3 are longer than the cis-; (ii) the RhCl bond lengths range from 2.268(4) (5) to 2.464(6) (3)Å; (iii) in the bis(carbene) complexes 4 and 5, as well

  由[Rh（μ-Cl）COD）} 2和烯四胺L 2 Me，L 2 Et，L 2 CH 2 Ph或L（2 323）CH 2 Ph）形成结晶络合物[RhCl（L R）3 ] [RCH 2 Ph（上1）或Et（3）]，[RCl的（COD）} 2 μL 2 （323）CH 2博士}]（2），或反式- [的RhCl（CO）（L R）2 ] [RCH 2 Ph（4）或Me（5）]已经以高收率[L获得ř  R和L （su323）R} （CH 2）2 ]。络合物2提供了一个桥接双（卡宾）双金属络合物的罕见实例，第一个化合物是从一个四烯胺衍生而来的。1-5的X射线结构表明：（i）1和3的互为反式-RhC碳键长于顺式-；（ii）RhCl键长在2.268（4）（5）至2.464（6）（3）Å之间；（iii）在双（卡宾）配合物4和5以及2中，五元几乎为平面的环（或2的片段）大致正交于含有Rh，Cl和C
• Transition-metal nitrosyl compounds. Part IV. Nitrosyl halide derivatives of rhodium(I) and iridium(I)
  作者：G. R. Crooks、B. F. G. Johnson

  DOI：10.1039/j19700001662

  日期：——

  = Cl or Br) have been prepared by the reactions of the nitrosyl halides. NOX, with [RhX(C8H12)]2 in dichloromethane or chloroform. An iridium mononitrosyl complex IrCl2(NO)(C8H12) has been prepared by the reaction of NOCl with [IrCl(C8H12)]2 in chloroform. These compounds are useful precursors for the preparation of the five-co-ordinate nitrosyl complexes MX2(NO)L2(L = Ph3P or Ph3As, X = Cl or Br) by

  聚合的单亚硝酰基配合物[Rh（NO）X 2 ] n（X = Cl或Br）是通过亚硝酰基卤化物的反应制备的。含[RhX（C 8 H 12）] 2的二氯甲烷或氯仿中的NOX 。通过使NOCl与[IrCl（C 8 H 12）] 2在氯仿中反应，制备铱单亚硝酰基络合物IrCl 2（NO）（C 8 H 12）。这些化合物是制备五配位亚硝酰基配合物MX 2（NO）L 2（L = Ph 3 P或Ph 3的有用前体As，X = Cl或Br）与Ph 3 P或Ph 3 As反应。在Ph 3 P或Ph 3存在下[Rh（NO）X 2 ] n或IrCl 2（NO）（C 8 H 12）与Lil或LiBr的易位反应。得到化合物MX 2（NO）L 2（ X = Cl，Br或I）。关于4000-200 cm区域的Ir数据。介绍了–1并讨论了可能的结构。
• Cyclopropenylylidene-Stabilized Diaryl and Dialkyl Phosphenium Cations: Applications in Homogeneous Gold Catalysis
  作者：Jekaterina Petuškova、Hans Bruns、Manuel Alcarazo

  DOI：10.1002/anie.201100338

  日期：2011.4.11

  Cationic but electron‐rich: Cyclopropenylylidene‐stabilized phosphenium cations exhibit the electron richness of classical trialkyl and triaryl phosphines even though they carry a positive charge stemming from a cationic substituent directly bonded to the phosphorous atom. These two facts have been exploited to synthesize gold catalysts that can be easily recycled after use.

  阳离子但富电子的：环丙烯基亚丙基稳定的阳离子显示出经典的三烷基和三芳基膦的电子富集，即使它们带有直接与磷原子键合的阳离子取代基所带的正电荷。已经利用这两个事实来合成金催化剂，该金催化剂在使用后可以容易地回收。