12130-88-0

Usage

Uses

Used in Organic Synthesis:
Pentamethylcyclopentadienylrhenium tricarbonyl is used as a catalyst for various organic synthesis reactions, facilitating the reduction of double bonds and the formation of carbon-carbon bonds. Its catalytic properties are instrumental in the synthesis of complex organic molecules, contributing to the advancement of organic chemistry.
Used in Organometallic Chemistry:
In the field of organometallic chemistry, Pentamethylcyclopentadienylrhenium tricarbonyl is utilized as a precursor or intermediate in the synthesis of other organometallic compounds. Its unique structure allows for the exploration of new reactions and the development of novel organometallic materials.
Used in Inorganic Chemistry:
Pentamethylcyclopentadienylrhenium tricarbonyl also finds applications in inorganic chemistry, where it is employed in the preparation of inorganic complexes and materials. Its potential use in this field is driven by the compound's ability to form stable coordination compounds with various inorganic ligands.
Used in Catalyst Development:
PENTAMETHYLCYCLOPENTADIENYLRHENIUM TRICARBONYL is used as a catalyst in the development of new chemical processes, where its reactivity and stability contribute to the efficiency and selectivity of the reactions. Its role in catalyst development is crucial for the creation of more sustainable and efficient chemical production methods.
Used in Research and Development:
Pentamethylcyclopentadienylrhenium tricarbonyl is utilized in research and development settings to explore its properties and potential applications further. Its unique characteristics make it an interesting subject for studies in organometallic and inorganic chemistry, potentially leading to new discoveries and applications.

InChI:InChI=1/C10H15.3CO.Re/c1-6-7(2)9(4)10(5)8(6)3;3*1-2;/h1-5H3;;;;

Upstream product

• 94405-82-0 (C₅(CH₃)5)Re(CO)(COOH)(N₂C₆H₄OCH₃) 
• 14285-68-8 decacarbonyldirhenium⁽⁰⁾ 
• 4045-44-7 1,2,3,4,5-pentamethylcyclopentadiene 
• 156042-18-1 trans-(η(5)-pentamethylcyclopentadienyl)(dicarbonyl)(dihydrido)rhenium 
• 201230-82-2 carbon monoxide 
• 917-54-4 methyllithium 

Downstream Products

• 847019-91-4 trans-[(η5-C5Me5)Re(CO)2(3-C6H3Cl-4-Me)Cl] 
• 847019-90-3 trans-[(η5-C5Me5)Re(CO)2(C6H3ClF)Cl 
• 847019-93-6 trans-[(η5-C5Me5)Re(CO)2[C6H3Cl(OCH3)]Br 
• 847019-89-0 trans-[(η5-C5Me5)Re(CO)2[C6H3Cl(OCH3)]Cl 
• 847019-92-5 trans-[(η5-C5Me5)Re(CO)2(C6H3ClCF3)Cl 
• 894100-55-1 trans-[(η5-C5Me5)Re(CO)2(3-C6H4Cl)Cl] 
• 653000-24-9 trans-(η5-C5Me5)Re(CO)2(2-methyoxy-4,5-dichlorophenyl)chloride 
• 242816-74-6 Re(C₅(CH₃)5)(CO)2(C₆F₅)2 
• 242816-73-5 Re(C₅(CH₃)5)(CO)2(H)(C₆F₅) 
• 242816-75-7 Re(C₅(CH₃)5)(CO)2(C₆F₅)(C₆F₄H) 

Relevant academic research and scientific papers

Reactions of cationic complex [(η5-C5Me5)Re(CO)3I]+ with primary amines leading to cyclic carbamoyl complexes

The reaction of cationic complex [(5-C5Me5)Re(CO)3I]+ with aliphatic and aromatic primary amines unexpectedly produced the chelated carbamoyl species trans-(5:1-C5Me4CH2NRC({double bond, long}O))Re(CO)2(I) (1, R = Me; 2, R = Pr; 3, R = Ph; 4, R = p-tolyl). The 1-coordination of carbamoyl moiety linkages to a methylene group of tetramethylcyclopentadienyl ligand was confirmed by X-ray crystallography of complex 3. All the complexes were isolated as pure samples and fully characterized by IR, 1H and 13C NMR spectroscopies, mass spectrometry and elemental analysis.

Syntheses, structures and reactivities of [CpTc(CO)3X] + and [CpRe(CO)3X]+

We have synthesized the [Cp*MIII(CO)3Br] + complexes (M = Re, 99Tc) and studied their basic chemistry in water and in organic solvents in order to understand if these complexes could be synthons for the preparation of new Re- and 99Tc-based cyclopentadienyl cores for (radio)pharmaceutical applications. The [Cp*MIII(CO)3Br]Br [M = Re (1), 99Tc (1a)] complexes were obtained in nearly quantitative yield from the reaction of the corresponding [Cp*MI(CO)3] with Br2 in cold toluene. Compounds 1 and 1a are photo- and thermally unstable and undergo rapid, bromide concentration-dependent redox reactions at room temperature generating the stable [Cp*MIII(CO) 3Br][(CO)3MI(μ-Br)3M I(CO)3] [M= Re (2), 99Tc (2a)] species as main products. Reaction of 1 with AgSbF6 gives rise to the redox-stable complex [Cp*ReIII(CO)3-Br]SbF3 (3). In water, 1 and 1a produces a mixture of cis/trans-[Cp*MIIIBr 2(CO)2] isomers [M = Re (cis/trans-4), 99Tc (cis/trans-4a)] via CO release. In methanol, 3 reacts with the solvent to generate the methoxycarbonyl complex trans-[Cp*ReIII(CO) 2Br(COOCH3)] (5). Compound 5 is stable under basic conditions. In acidic media it is converted into [Cp*Re I-(CO)3] as the major product. Kinetic studies with 13C labelled formic acid indicate that formic acid, generated from rapid hydrolysis of methyl formate released from 5, is the reducing agent and the source of CO. Reaction of 1 with 3-fluorobenzyl alcohol (3-FBA), chosen as a simple model of fluorouracil, gives the corresponding alkoxycarbonyl complex [Cp*ReIII-(CO)2Br(COOCH2-C 6H4F)] (7). Under acidic conditions 7 rapidly releases 3-FBA to give [Cp*ReI(CO)3]. Compounds 2, 2a, cis-4, trans-4a and 5 were structurally characterized. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Role of the transition metal in metallaborane chemistry. Reactivity of (Cp*ReH2)2B4H4 with BH3·thf, CO, and Co2(CO)8

The reaction of Cp*ReCl4, [Cp*ReCl3]2, or [Cp*ReCl2]2 (Cp* = η5-C5Me5) with LiBH4 leads to the formation of 7-skeletal-electron-pair (7-sep) (Cp*ReH2)2(B2H3)2 (1) together with Cp*ReH6. Compound 1 is metastable and eliminates H2 at room temperature to generate 6-sep (Cp*ReH2)2B4H4 (2). The reaction of 2 with BH3·thf produces 7-sep (Cp*Re)2B7H7, a hypoelectronic cluster characterized previously. Heating of 2 with 1 atm of CO leads to 6-sep (Cp*ReCO)(Cp*ReH2)B4H4 (3). Both 2 and 3 have the same bicapped Re2B2 tetrahedral cluster core structure. Monitoring the reaction of 2 with CO at room temperature by NMR reveals the formation of a 7-sep, metastable intermediate, (Cp*ReCO)(Cp*ReH2)(B2H3)2 (4), which converts to 3 on heating. An X-ray structure determination reveals two isomeric forms (4-cis and 4-trans) in the crystallographic asymmetric unit which differ in geometry relative to the disposition of the metal ancillary ligands with respect to the Re-Re bond. The presence of these isomers in solution is corroborated by the solution NMR data and the infrared spectrum. In both isomers, the metallaborane core consists of fused B2Re2 tetrahedra sharing the Re2 fragment. On the basis of similarities in electron count and spectroscopic data, 1 also possesses the same bitetrahedral structure. The reaction of 2 with Co2(CO)8 results in the formal replacement of the four rhenium hydrides with a 4-electron Co2(CO)5 fragment, thereby closing the open face in 2 to produce the 6-sep hypoelectronic cluster (Cp*Re)2Co2(CO)5B4H4 (5). These reaction outcomes are compared and contrasted with those previously observed for 5-sep (Cp*Cr2)2B4H8.

An investigation into the reactivity of organometallic noble gas complexes: A time-resolved infrared study in supercritical noble gas and alkane solution at room temperature

A study investigated the effect of cyclopentadienyl ring substituents on the reactivity of the Group 7 half-sandwich complexes, (η5-C5R5)M(CO)2L (M = Mn and Re; R = H, Me and Et (Mn only); L = Kr and Xe) toward CO in supercritical fluid solution at room temperature. The steric bulk of the three types of ring substituent steadily increased in the order H 5-C5R'5)Mn(CO)2Xe (R' = H and Me) and (η5-C5R'5)Mn(CO)2Kr had very similar reactivity toward CO, while (η5C5Et5)Mn(CO)2L (L = Xe and Kr) were approximately twice as reactive. Experiments with the manganese xenon complexes suggested that the noble gas complexes react with CO in supercritical solution via a dissociative mechanism. This reaction mechanism was further evidenced by temperature dependence studies where the enthalpies of activation were calculated for these noble gas complexes and the analogous alkane complexes.

Synthesis and X-ray structure of the rhenium methyl complex trans-Cp*Re(CO)2(Me)I and a study of the products of photolysis of the rhenium alkyl methyl and dimethyl complexes Cp*Re(CO)2(Me)R (R = Ph, p-Tolyl, Me) under CO

Reaction of Cp*Re(CO)2I2 with methylcopper affords cis-Cp*Re(CO)2(Me)I, which converts to the trans isomer on prolonged reaction or in the presence of neutral alumina. The X-ray structure of the trans isomer has been determined. The related chloro complexes Cp*Re-(CO)2(Me)Cl and Cp*Re(CO)2(p-tolyl)Cl are formed in the photolyses of compounds 3 and 1 (below) in CCl4. Photolysis of Cp*Re(CO)2(Me)R (R = p-tolyl (1), Ph (2), Me (3)) in the presence of CO has been carried out in hydrocarbons, CCl4, and benzene-d6. In hydrocarbons, 1 and 2 produce Cp*Re(CO)3, CH4, and either toluene or benzene, respectively; 3 produces Cp*Re-(CO)3 and CH4. In benzene-d6 1 gave CH3D and toluene-4-d, and 3 gave mainly CH3D. These results are consistent with a general scheme involving successive homolysis of the metal-methyl and metal-aryl bonds to give methyl and aryl radicals that abstract H or D from the solvent and carbonylation of the rhenium dicarbonyl fragment. Products known or expected to arise from further photolysis of Cp*Re(CO)3 in benzene-d6, such as Cp*2Re2(CO)3, Cp*2Re2(CO)5, and Cp*Re(CO)2(η2-C6D6), were also found. Photolysis of 1 in CCl4 in the presence or absence of CO gave CH3Cl and Cp*Re(CO)2(p-tolyl)Cl, but no p-chlorotoluene, indicating the preferential homolysis of the Re-Me bond and the rapid scavenging of the subsequent radicals by the chlorinated solvent. Photolysis of the dimethyl complex 3 gave CH3Cl and some evidence of a small amount of Cp*Re(CO)2(Me)Cl, but the major rhenium product was Cp*Re(CO)2Cl2, consistent with the more facile homolysis of both Re-Me bonds in 3. Production of small amounts of CH2D2 (in benzene-d6) and CH4 and CH2Cl2 (in CCl4) are discussed in terms of a competing pathway. Notably, in none of these photolyses were there observed other than trace amounts of products such as p-xylene, which would be expected to be major products if reductive elimination were to occur.

Reaction of Cp*(CO)2Re=Re(CO)2Cp* in THF with diethyl fumarate produces Cp*Re(CO)3 and Cp*Re(CO)(η2-(E)-EtO2CCH=CHCO 2Et)(THF)

The rhenium dimer complex Cp*(CO)2Re=Re(CO)2Cp* (1) (Cp=C5Me5) reacted in THF with diethyl fumarate in a fragmentation reaction to form Cp*Re(CO)3 (3) and Cp*Re(CO)(η2-(E)-EtO2CCH=CHCO 2Et)(THF) (6). Reaction of 6 with CO resulted in substitution of the THF ligand with CO to form the alkene complex Cp*Re(CO)2(η2-(E)-EtO2CCH=CHCO 2Et) (7). Variable temperature 1H-NMR spectroscopy of 7 showed that rotation of the alkene ligand is slow below -50°C.

Synthesis, X-ray crystal structure and photochemistry of (η5-pentamethylcyclopentadienyl) (dicarbonyl) (dihydrido) rhenium in cyclohexane and liquid xenon solutions and in low temperature media at about 12 K

An improved synthesis of (η5-C5Me5)Re(CO)2(H)2 has been devised (yield 88%) via (η5-C5Me5)Re(CO)3 and (η5-C5Me5)-Re(CO)2(Br) 2. An X-ray crystallographic determination has shown that the hydrido ligands occupy trans positions, in confirmation of IR and NMR measurements. The properties and reactions of trans-(η5-C5Me5)Re(CO)2(H) 2 and related compounds (η5-C5Me5)Re(CO)2(X)(Y) (X = H, Me; Y = H, Me, Cl) are described. The solution photochemistry of trans-(η5-C5Me5)Re(CO)2(H) 2 in cyclohexane at 298 K and in liquid xenon at 200 K, including studies under D2, indicate that the primary photoproduct is the cis isomer and that trans to cis interconversion, which can be reversed thermally, is an intramolecular process. Photochemical studies of (η5-C5Me5)Re(CO)2(N2) in liquid Xe under H2 and D2 pressures at 200 K gave cis-(η5-C5Me5)Re(CO)2(H) 2 and cis-(η5-C5Me5)Re(CO)2(D) 2, respectively. Matrix isolation studies at about 12 K, including 13CO labelling, confirmed that the photoisomerisation process is an intramolecular process since no ejected CO is observed and no 13CO uptake occurred. Subsequent photolysis affords H2 and CO ejection yielding (η5-C5Me5)Re(CO)2 and (η5-C5Me5)Re(CO)(H)2, respectively. In N2 and CO matrices the subsequent photolysis also yielded (η5-C5Me5)Re(CO)2(N2) and (η5-C5Me5)Re(CO)3 but in CH4 matrices there was no evidence of C-H photoactivation to yield (η5-C5Me5)Re(CO)2(CH 3)(H). Reversal from cis to trans could not be observed for gas matrices but was observed at near ambient temperatures for the cis isomer produced at about 12 K in Nujol mull media.

[{Cp*(Cl)Re}2(μ-CO)2](Re ≡ Re), a dinuclear rhenium(II) complex with cis configuration of the terminal Cl atoms

The reaction of [{Cp*(OC)2Re}2](Re = Re) (1), Cp* = C5Me5, with CH2Cl2 yields the dinuclear rhenium complexes [{Cp*(Cl)Re}2(μ-CO)2](Re ≡ Re) (2) with cis orientation of the Cl atoms, [{Cp*(OC)2Re}2(μ-CH2)](Re-Re) (3), a complex with a bridging CH2-carbene ligand, and [{Cp*(OC)2Re}2(μ-C=CH2)](Re-Re) (4), a μ-vinylidene(alkenylidene) compound. The structure of 2 has been confirmed by a single crystal X-ray structure determination. Starting with [Cp*Re-(CO)2(thf)] (6) instead of 1 the reaction with CH2Cl2 affords cis-[Cp*Re(CO)2(Cl)(CH2Cl)] (7) by oxidative addition of dichloromethane.