12092-47-6

Basic information

• Product Name: Chloro(1,5-cyclooctadiene)rhodium(I) dimer
• Synonyms: Bis(1,5-cyclohexadiene)-mu,mu'-dichlorodirhodium;Bis(cycloocta-1,5-diene)dichlorodirhodium;Chloro(1,5-cyclooctadiene)rhodium dimer;Dichloro-bis-1,5-cyclooctadiene dirhodium;Di-mu-chlorobis(1,5-cyclooctadiene)dirhodium;di-mu-chlorobis[(1,2,5,6-eta)-1,5-cyclooctadiene]di-rhodiu;Rhodium 1,5-cyclooctadiene chloride dimer;Rhodium chloro(cycloocta-1,5-diene) dimer
• CAS NO: 12092-47-6
• Molecular Formula: C₁₆H₂₄Cl₂Rh₂
• Molecular Weight: 493.08
• EINECS: 235-157-6
• Product Categories: Rh (Rhodium) Compounds;Catalysts for Organic Synthesis;Classes of Metal Compounds;Homogeneous Catalysts;Metal Complexes;Synthetic Organic Chemistry;Transition Metal Compounds;organometallic complexes;Morpholines/Thiomorpholines ,Isoxazoles;Rh
• Mol File: 12092-47-6.mol
• Article Data: 20

Chemical Properties

• Melting Point: 243 °C (dec.)(lit.)
• Boiling Point: 153.5 °C at 760 mmHg
• Flash Point: 31.7 °C
• Appearance: Orange to orange-brown/Crystals or Crystalline Powder
• Density: 1.94[at 20℃]
• Vapor Pressure: 0Pa at 25℃
• Storage Temp.: 2-8°C
• Solubility: Soluble in chloroform, dichloromethane, and methanol. Sparingly
• Water Solubility: 1.56g/L at 20℃
• Sensitive: Air Sensitive & Hygroscopic
• Stability: hygroscopic
• CAS DataBase Reference: Chloro(1,5-cyclooctadiene)rhodium(I) dimer(CAS DataBase Reference)
• NIST Chemistry Reference: Chloro(1,5-cyclooctadiene)rhodium(I) dimer(12092-47-6)
• EPA Substance Registry System: Chloro(1,5-cyclooctadiene)rhodium(I) dimer(12092-47-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39
• WGK Germany: 3
• F: 3
• TSCA: Yes
• Hazardous Substances Data: 12092-47-6(Hazardous Substances Data)

Usage

Reaction

Catalyst for coupling 1,3-dienes with activate methylene compounds. Rhodium source for various asymmetric hydrogenation systems and asymmetric hydrosilylation of ketones. Rhodium source for asymmetric reductive aldol reaction. Cis-hydroboration of terminal alkynes. Rhodium source for [5 + 2] additions. Highly enantioselective for [2+2+2] carbocyclization reactions. Enantioselective hydroboration of cyclopropenes.

Chemical Properties

orange crystals

Uses

Different sources of media describe the Uses of 12092-47-6 differently. You can refer to the following data:
1. It is a widely used precursor to homogeneous catalysts. This is a chiral catalyst capable of asymmetrically hydrogenating certain prochiral alkenes. Chloro(1,5-cyclooctadiene)rhodium(I) dimer is also used in the synthesis of other metal ligands for use in catalysis.
2. Chloro(1,5-cyclooctadiene)rhodium(I) dimer ([Rh(COD)Cl]2) can be:Employed for the synthesis of rhodium complex of heterocyclic carbenes (NHCs).Modified and coated on the surface of ferrite magnetic nanoparticles for catalyzing hydroformylation reaction of olefins. Used for the synthesis of triple-layer structure to be used as a ring-opening polymerization catalyst.As an effective catalyst for dehydrogenation of amine-borane adducts (hydrogen storage materials) such as ammonia-borane.

General Description

This product has been enhanced for catalytic efficiency.

Flammability and Explosibility

Notclassified

InChI:InChI=1/2C8H12.2ClH.2Rh/c2*1-2-4-6-8-7-5-3-1;;;;/h2*1-2,7-8H,3-6H2;2*1H;;/q;;;;2*+1/p-2/b2*2-1-,8-7-;;;;/r2C8H12.2ClRh/c2*1-2-4-6-8-7-5-3-1;2*1-2/h2*1-2,7-8H,3-6H2;;/b2*2-1-,8-7-;;

Synthetic route

(2-methylallyl)palladium-chloride dimer + chlorocycloocta-1,5-diene(diphenyl-2-pyridylphosphine)rhodium(I) (135973-06-7) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + {Pd(η3-methylallyl)(2-(diphenylphosphino)pyridine)Cl} (135973-14-7)

Conditions	Yield
In dichloromethane (N2), after addn. stirred for 2 h, reduced volume, added petroleum ether-diethyl ether (1:1); filtered, washed with diethyl ether, dried in vac., ((C8H12)RhCl)2 recovered from mother liquor; elem. anal.;	A n/a B 95%

rhodium trichloride hydrate + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6)

Conditions	Yield
In ethanol; water react. in ethanol/water in a sealed Teflon container (microwave oven, 2450 MHz, 500 W, 50 sec);	91%

rhodium trichloride hydrate → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6)

Conditions	Yield
With cyclooctadiene In ethanol; water in a modified reflux microwave apparatus RhCl3 reacts with cyclooctadiene in EtOH-H2O (5:1) (react. time: 25 min);	87%

rhodium(III) chloride trihydrate + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6)

Conditions	Yield
In ethanol; water in a microwave oven (Fischer-Porter reaction vessel) at 140°C for 0.5 min; elem. anal.;	84%
In ethanol; water under N2 or Ar, reflux of soln. overnight; soln. is cooled, recrystn. from CH2Cl2/hexane;	82%
In ethanol A soln. of RhCl*3H2O and COD is refluxed for 45 min until a ppt. sepd. out.; Ppt. is washed with CH3OH, dried at 80°C for 30 min, recrystd. from petroleum ether (60-80°C).;

dichloro(cycloocta-1,5-diene)palladium (II) (12107-56-1) + Rh(C8H12)(C5H3N(P(C6H5)2)(OCH3))Cl (143890-17-9) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + {Pd(C5H3N(P(C6H5)2)(OCH3))Cl2}2 (143890-27-1)

Conditions	Yield
In dichloromethane (N2); dropwise addn. of the Pd-complex to the Rh-complex in CH2Cl2, stirring for 1 h; the volume of the soln. is reduced, addn. of diethyl ether, filtration, washing (diethyl ether), drying in vac., elem. anal.;	A 71% B 78%

RhCl3*(2-3)H2O + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6)

Conditions	Yield
In ethanol; water N2-atmosphere; addn. of RhCl3 to soln. of COD, refluxing (5 h), coolingto room temp. (pptn.); collecting, washing (cold H2O and EtOH), drying (1 h in air, then room temp., vac., overnight);	77%

rhodium(III) chloride trihydrate + rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + RhCl2{C6H3(CH2NMe2)2-o,o'} (10049-07-7)

Conditions	Yield
In dichloromethane reflux;	A 0% B 0%
In benzene reflux;	A 0% B 0%

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) + zirconium(IV) chloride (10026-11-6) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + ZrCl3{C6H3(CH2NMe2)2-o,o'} (115338-71-1)

Conditions	Yield
In dichloromethane instant reaction; no sepn. of metal-contg. products (similar soly.);
In benzene instant reaction; no sepn. of metal-contg. products (similar soly.);

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + HgCl{C6H3(CH2NMe2)2-o,o'} (81352-52-5)

Conditions	Yield
With HgCl2 In dichloromethane instant reaction; no sepn. of metal-contg. products (similar soly.);
With HgCl2 In benzene instant reaction; no sepn. of metal-contg. products (similar soly.);

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + {m-(Me2(H)NCH2)2C6H4}Cl2 (63400-16-8)

Conditions	Yield
With HCl In benzene HCl is bubbled for 1 min through a soln. of Rh complex.; addn. of water, sepn. of layers; evapn. of benzene layer yields (RhCl(COD))2, ammonium salt of aryl compound is obtained from water layer.;	A >99 B >99

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) + rhodium(III)chloride (10049-07-7) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + RhCl2{C6H3(CH2NMe2)2-o,o'} (10049-07-7)

Conditions	Yield
In dichloromethane reflux;	A 0% B 0%
In benzene reflux;	A 0% B 0%

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) + iridium (III) chloride (10025-83-9) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + IrCl2{C6H3(CH2NMe2)2-o,o'}

Conditions	Yield
In dichloromethane reflux;	A 0% B 0%
In benzene reflux;	A 0% B 0%

rhodium{C6H3(CH2NMe2)2-o,o'}(1,5-cyclooctadiene) (115338-66-4) + tantalum pentachloride (7721-01-9) → di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium (12092-47-6) + TaCl4{C6H3(CH2NMe2)2-o,o'}

Conditions	Yield
In dichloromethane reflux;	A 0% B 0%
In benzene reflux;	A 0% B 0%

Upstream product

• 12080-32-9 dichloro(1,5-cyclooctadiene)platinum(ll) 
• 122658-53-1 {Rh(benzothiazole-2-thiolate)(CO)(triphenylphosphine)}2 
• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 124225-83-8 1,1’-((phenyl)methylene)bis(3,5-dimethyl-1H-pyrazole) 
• 5259-72-3 cyclo-octa-1,5-diene 
• 89178-74-5 (1,5-cyclooctadiene)chloro{bis{bis(trimethylsilyl)methyl}chlorophosphine}rhodium(I) 
• 89178-76-7 (1,5-cyclooctadiene)chloro{bis{bis(trimethylsilyl)methyl}methylphosphine}rhodium(I) 
• 185117-10-6 [RhCl(2,6-(C(H)=N-t-Bu)2C₅H₃N)(1,5-cyclooctadiene)] 
• 34710-33-3 cis-[bis(tert-butylisocyanide)dichloropalladium(II)] 
• 143890-17-9 Rh(C₈H₁₂)(C₅H₃N(P(C₆H₅)2)(OCH₃))Cl 
• 12107-56-1 dichloro(cycloocta-1,5-diene)palladium (II) 
• 26042-63-7 silver(I) hexafluorophosphate 
• 14243-64-2 (triphenylphosphine)gold(I) chloride 
• 135973-06-7 chlorocycloocta-1,5-diene(diphenyl-2-pyridylphosphine)rhodium(I) 

Downstream Products

• 82861-87-8 RhCl(trimethylphosphine)(bis(diphenylphosphino)methane) 
• 25777-46-2 {Rh(P(OC₂H₅)3)4}⁽¹⁺⁾*B(C₆H₅)4^(1-)={Rh(P(OC₂H₅)3)4}B(C₆H₅)4 
• 57109-24-7 Rh(PH(C₂H₅)2)4⁽¹⁺⁾*B(C₆H₅)4^(1-)={Rh(PH(C₂H₅)2)4}B(C₆H₅)4 
• 120659-57-6 (η4-1,5-cyclooctadiene)bis{diphenyl(2-methoxyethyl)phosphine-P}rhodium(I)-tetraphenylborate 
• 120691-12-5 cis{Rh(PPh₂CH₂CH₂NMe₂)2}BPh₄ 
• 127261-08-9 chloro(η4-1,5-cyclooctadiene){(2-methoxyethyl)diphenylphosphane}rhodium(I) 
• 123880-99-9 (η4-1,5-cyclooctadiene)-cis-bis{(2-methoxyethyl)diphenylphosphane}rhodium(I)-hexafluoroantimonate 
• 117939-76-1 Rh(C₈H₁₂)(C₆H₄SO₃)2PCH(CH₃)CH₂CH(CH₃)P(C₆H₄SO₃)2^(3-)*4Na⁽¹⁺⁾=Na₄Rh(C₈H₁₂)(C₆H₄SO₃)2PCH(CH₃)CH₂CH(CH₃)P(C₆H₄SO₃)2⁽¹⁺⁾ 
• 104335-70-8 (chloro)(1,5-cyclooctadiene){o-(diphenylphosphino)-N-benzylaniline}rhodium(I) 
• 36103-68-1 (Me₂PhP)3RhCl 
• 125820-90-8 (1,5-cyclooctadiene)rhodium(I)Cl(N-benzyl-imidazole) 
• 126586-34-3 {Rh(cyclooctadiene)Cl}2(μ-1,4-bis(diphenylphosphino)butane) 
• 126586-36-5 {Rh(cyclooctadiene)Cl}2(μ-1,6-bis(diphenylphosphino)hexane) 
• 64828-26-8 {Rh(Cl)(CO)(μ-1,6-bis(diphenylphosphino)pentane)}2 

Relevant articles and documents

Application of microwave dielectric loss heating effects for the rapid and convenient synthesis of organometallic compounds

Diolefin-rhodium(I) and -iridium(I) complexes have been synthesised in a sealed Teflon container by use of microwave heating.The products are obtained in excellent yields and in less than 1 minute compared with many hours by conventional reflux techniques

Immobilized chiral rhodium nanoparticles stabilized by chiral P-ligands as efficient catalysts for the enantioselective hydrogenation of 1-phenyl-1,2-propanedione

This work reports the efficient synthesis of enantio-enriched alcohols by asymmetric hydrogenation of 1-phenyl-1,2-propanedione using chiral nanoparticles (NPs) supported on SiO2. The chiral catalysts were synthesized by reducing the [Rh(μ?OCH3)(C8H12)]2 precursor under H2 in the presence of P-chiral ligands as stabilizers and SiO2 as support. Synthesis of catalysts in mild conditions was performed from labile organometallic precursor and chiral ligands provided small and well defined chiral nanoparticles (≤ 3 nm). The catalysts were characterized by XPS, HR-TEM, EDS, XRD and N2 physisorption isotherm. The physical chemical properties of the materials were correlated with the catalytic results obtained in the asymmetric hydrogenation of 1-phenyl-1,2-propanedione. In 1-phenyl-1,2-propanedione hydrogenation the best results using chiral catalysts allowed 98% conversion and enantiomeric excess of 67% to (R)-1-hydroxy-1-phenyl-propan-2-one and 59% for (R)-2-hydroxy-1-phenylpropan-1-one. Catalyst recycling studies revealed that chiral nanoparticles immobilized on SiO2 are stable. These catalysts do not need extra amount of chiral modifier or inducer added in situ and could be reused without loss of enantioselectivity.

Synthesis of M2Rh2 Bis(μ3-carbon dioxide) complexes from the reaction between [Rh(OH) (η4-COD)]2 and cationic metal carbonyls

The M2Rh2 bis(μ3-CO2) complexes [Cp*(CO)(NO)Re(CO2)Rh(η4-cod)]2 (1) and [Cp*(CO)2-MCO2Rh(η4-cod)] 2, M = Fe (2) and Ru (3), were synthesized in moderate to high yields from treating [Rh(OH)(η4-cod)]2 (cod = 1,5-cyclooctadiene) with the carbonyl salts Cp*(L)(CO)2M+ (L = CO, M = Fe, Ru; L = NO, M = Re) and a base. [An alternative synthesis of 1 and its crystallographic structure determination has been reported.] Although details on using several bases in the synthesis of 2 are reported, the use of volatile EtMe2N in excess as the base is especially useful. IR and NMR spectral data are in accord with a M2Rh2 bis(μ3-CO2) core for 2 and 3: they retain two μ3-[η1-C(M):η1-O(Rh):η 1-O′(Rh′)] carboxylate ligands that resemble those that were found for 1 and the Rh(I) carboxylates [(RCO2)Rh(diene)]2. Complexes 2 and 3 with their open-book structures are not fluxional at room temperature. Complex 2, its norbornadiene analogue, [Cp*(CO)2FeCO2Rh(η4-nbd)]2 (4), and their 13C-labeled derivatives also are accessible from reactions of Cp*(CO)2FeCO2K [or Cp*(CO)2-Fe13CO2K] with [Rh(OSO2CF3)(η4-cod)x. [Cp*(CO)2Fe(13CO2)Rh(η 4-diene)]2 [diene = cod (2-13C); nbd (4-13C)] underwent carboxylate-carbonyl label shuttle to yield 1:1 mixtures of [Cp*(CO)(13CO)FeCO2Rh(diene)]2 (2a-C13) and 4a-C13. IR spectral assignments for the metallocarboxylate νOCO absorptions are also presented.

Rhodium complexes of a chelating bisphosphoniobenzophospholide cation

The 1-(diphenyl(2-diphenylphosphinoethyl)phosphonio)-3-triphenylphosphoniobenzo[c]ph ospholide cation 1 reacts with [RhCl(C2H4)2]2 to form a dinuclear chelate complex, [RhCl(κ2-P(?2), P′(?)-1)]2 (5). Treatment of 5 with PPh3 affords mononuclear [RhCl(PPh3)(κ2- P(?2),P′(?3)-1)] (8), whereas reaction with 1,5-cyclooctadiene proceeds via cleavage of the Cl bridges to give [RhCl(cod)(κ-P(?3)-1)] (6). The chelating binding mode of 1 can be reconstituted by abstraction of chloride with TlOTf to give the dicationic complex [Rh(cod)(κ2-P(?2),P′(?3 )-1)]2+ (7). All complexes have been characterized by 1H, 31P, and 103Rh NMR spectroscopy, and 5[BPh4]2 was characterized as well by single-crystal X-ray diffraction. The structural parameters and metal NMR data confirm the different electronic properties of the two types of phosphorus centers in 1 and support in particular the assumption of distinct ?-acceptor character for the ?2-P atom, which should render the complexes potentially interesting precatalysts for hydroformylation. In accord with this hypothesis, complexes 5[BPh4]2 and 7[BPh4]2 display good activities and chemoselectivities as catalysts for the hydroformylation of 1-hexene at room temperature, even though the regioselectivities for n-aldehydes are low.

Polyoxoanion-supported catalyst precursors. Synthesis and characterization of the iridium(I) and rhodium(I) precatalysts [(n-C4H9)4N]5Na 3[(1,5-COD)M·P2W15Nb3O 62] (M = Ir, Rh)

The reaction of the triniobium-substituted polyoxometalate [(n-C4H9)4N]9P2W 15Nb3O62 with an equimolar amount of [Ir(1,5-COD)(CH3CN)2]BF4 or [Rh(1,5-COD)(CH3CN)2]BF4 (1,5-COD = 1,5-cyclooctadiene) leads to the formation of the air-sensitive polyoxometalate-supported organometallic complexes [(1,5-COD)IrP2W15Nb3O62] 8-, 1, and [(1,5-COD)Rh·P2W15Nb3O 62]8-, 2. These complexes were isolated as their mixed 5[(n-C4H9)4N]+/3Na+ salts and have been characterized by 1H, 13C, 31P, and 183W NMR spectroscopy as well as IR spectroscopy, sedimentation-equilibrium molecular-weight measurements, and complete elemental analyses. Additional studies of 1 by 17O NMR demonstrate that the iridium binds in overall average C3v (pseudo) symmetry to the Nb3O93- minisurface (pseudo due to the 2-fold axis in 1,5-COD and thus the local Cs symmetry at iridium). For 2, the results of the 17O NMR studies are definitive in showing that 2 can also be successfully 17O-enriched in the niobium-oxygen sites. However, the 17O NMR data subsequently acquired for 2 require the formulation of two or more (possibly rapidly interconverting) support-site isomers in solution. These 17O NMR results provide direct evidence for the M-ONb2 bonding between [(1,5-COD)M]+ (M = Ir, Rh) and P2W15Nb3O629- in solution, where catalysis beginning with 1 and 2 as a precatalyst has been demonstrated.