12079-65-1

Usage

Uses

Used in Fuel Industry:
Cyclopentadienylmanganese tricarbonyl is used as an antiknock agent for improving the performance and efficiency of gasoline engines. It helps to prevent knocking or pinging sounds in engines, which can cause damage to the engine components.
Used in Gasoline Production:
Cyclopentadienylmanganese tricarbonyl is used as an octane enhancer for gasoline, particularly for unleaded gasoline. It helps to increase the octane rating of gasoline, which is a measure of the fuel's resistance to knocking or pinging during combustion.
Used in Organic Synthesis:
Cyclopentadienylmanganese tricarbonyl is used as an important raw material and intermediate in organic synthesis. It is involved in various chemical reactions, such as carbonylation, hydroformylation, and olefin polymerization, to produce a wide range of organic compounds.
Used in Pharmaceutical Industry:
Cyclopentadienylmanganese tricarbonyl is used as a pharmaceutical intermediate in the synthesis of various drugs and pharmaceutical compounds. Its unique chemical properties make it a valuable component in the development of new medications and therapies.
Chemical Properties:
Cyclopentadienylmanganese tricarbonyl is characterized by its bright yellow color and crystalline structure. It appears as yellow crystals or crystalline chunks. CYCLOPENTADIENYLMANGANESE TRICARBONYL is known for its sublimation properties, which allow it to transition from a solid to a gas at temperatures between 75-77°C. Additionally, it exhibits slight solubility in water, making it suitable for use in various chemical processes and applications.

Reactivity Profile

MANGANESE CYCLOPENTAHIENYL TRICARBONYL is combustible. Heating causes evolution of carbon monoxide and other toxic or irritating gases. Heating in a confined space causes a rise in pressure with the risk of bursting. Incompatible with oxygen.

Hazard

Toxic material absorbed by skin. Central nervous system impairment and skin irritant.

Health Hazard

Manganese cyclopentadienyl tricarbonyl (MCT) causes convulsions and pulmonary edema in laboratory animals.

Safety Profile

A poison by ingestion, inhalation, intraperitoneal, and intravenous routes. A mild narcotic which can damage kidneys. When heated to decomposition it emits acrid smoke and irritating fumes. See also MANGANESE COMPOUNDS and CARBON MONOXIDE.

InChI:InChI=1/C5H5.3CO.Mn/c1-2-4-5-3-1;3*1-2;/h1-5H;;;;

Synthetic route

(C5H5)Mn(CO)2(CCSi2(CH3)6) → cymantrene (12079-65-1) + Bis(trimethylsilyl)ethyne (14630-40-1)

Conditions	Yield
in sealed tube at 200°C;	A 96% B 96%

η(5)-cyclopentadienyl(phenylvinylidene)(dicarbonyl)manganese + triethyl phosphite (122-52-1) → cymantrene (12079-65-1) + Cp(CO)2Mn{η2-PhCH=CHP(O)(OEt)2} + C5H5Mn(CO)(P(OC2H5)3)2 + [Mn(C5H5)(CO)2(P(OC2H5)3)] (12276-93-6) + (C5H5)(CO)[P(OCH2CH3)3]MnCCHC6H5 (64522-65-2)

Conditions	Yield
In hexane at 20°C under Ar, 1 h; evapn., chromy. (Al2O3, hexane/ether, then ether), recrystn. (hexane/ether)., elem. anal.;	A n/a B 96% C n/a D n/a E <1

dicarbonyl(η(5)-cyclopentadienyl)manganese(THF) + dimethylsulfide borane complex (13292-87-0) → cymantrene (12079-65-1) + [(η5-cyclopentadienyl)Mn(CO)2SMe2] (40674-63-3) + triphenylphosphine borane (2049-55-0)

Conditions	Yield
In toluene Inert atmosphere; Schlenk technique;	A n/a B n/a C 95%

η(5)-cyclopentadienyl(phenylvinylidene)(dicarbonyl)manganese + triisopropyl phosphite (116-17-6) → cymantrene (12079-65-1) + η5-cyclopentadienyl(dicarbonyl){η2-trans-1-(O,O-diisopropylphosphonato)-2-phenylethylene}manganese

Conditions	Yield
In hexane under Ar; addn. of P(O-i-Pr)3 hexane soln. to hexane soln. of complex, mixed 3h at 20°C; evapn., residue is dissolved in 1:1 hexane-diethyl ether mixt., chromd. (Al2O3), mixt. of CpMn(CO)3 and Cp(CO)2MnCCPhH, yellow band eluted with 1:1 hexane-methyl acetate, evapn. of solvent, oily residue treated with hexane/benzene, elem. anal.;	A n/a B 92%

cyclopentadienyl manganese tricarbonyl(1+) (59699-77-3) → cymantrene (12079-65-1)

Conditions	Yield
In dichloromethane Electrolysis; controlled potential electrolysis at 0.5 V, CH2Cl2/0.05 M N(C4H9)4B(C6F5)4; electrochemical IR-spectra;	90%

triiron dodecarbonyl (17685-52-8) + [dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + 1-butanethiol (109-79-5) + triethylamine (121-44-8) → cymantrene (12079-65-1) + (C5H5)Mn(CO)2(C(C6H5)S(C4H9))Fe(CO)3 + FeMn(4+)*C5H5(1-)*C6H5CSC4H9(3-)*5CO=(C5H5)Mn(CO)2(C(C6H5)S(C4H9))Fe(CO)3 + (C4H9S)2Fe2(CO)6

Conditions	Yield
In tetrahydrofuran N2-atmosphere; stirring (room temp., 40 min), Mn-compd. addn., stirring (-90 to -70°C, 3 h); evapn. (vac., -50 to -40°C), chromy. (alumina, -25°C, petroleum ether, petroleum ether / CH2Cl2 = 20 : 1, petroleum ether / CH2Cl2/ Et2O = 10 : 1 : 1), evapn. (vac.), recrystn. (petroleum ether / CH2Cl 2, -80°C); elem. anal.;	A 3% B 85% C 6% D 4%

(1-η(5)-cyclopentadienyl)(1,1-dicarbonyl)-μ-[(phenyl)ethenylidene][2-η(2)-bis(diphenylphosphino)ethane-PP']manganesepalladium + diiron nonacarbonyl → cymantrene (12079-65-1) + (1,1,2,2,2,3,3,3-octacarbonyl)(1-η(5)-cyclopentadienyl)-μ(3)-[1,2-η(1),3-η(2)-(phenyl)ethenylidene]-triangulo-manganesediiron + (1,1,1,1,2,2,2,2-octacarbonyl)[3-η(2)-bis(diphenylphosphino)ethane-PP']-triangulo-diironpalladium + (1,1,1,2,2,2,3,3,3-nonacarbonyl)-μ(4)-[1,η(2),2,3,4-η(1)-(phenyl)ethylidene][4-η(2)-bis(diphenylphosphino)ethane-PP']bis(triangulo)triironpalladium

Conditions	Yield
In benzene Ar-atmosphere, dry solvent; Fe-compd. addn. to soln. of Mn,Pd-complex, stirring (3 h, 20°C), soln. filtration through Al2O3, vacuum evapn.; oily residue dissoln. in hexane-benzene, chromy. (Al2O3/hexane-benzene),eluate fractions evapn.; elem. anal.;	A n/a B 71% C 5% D 9%

triiron dodecarbonyl (17685-52-8) + [dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + Benzeneselenol (645-96-5) → cymantrene (12079-65-1) + C5H5Mn(CO)2Fe(CO)3CC6H5SeC6H5 (349606-50-4) + (μ-PhSe)2Fe2(CO)6 (25987-99-9)

Conditions

Yield

With N(CH2CH3)3 In tetrahydrofuran (N2); addn. of selenium compd. and amine to a soln. of iron carbonyl in THF, stirring at room temp. for 10 min, cooling to -100°C, pouring to manganese complex, warming to -80°C, stirring for 7 h at -80to -50°C; evapn. at -50 to -40°C, column chromy (Al2O3, petroleum ether, petroleum ether/CH2Cl2 20:1, petroleum ether/CH2Cl2/Et2O 10:1:1), evapn., recrystn. (petroleum ether/CH2Cl2, -80°C); elem. anal.;

A 5% B 66% C 24%

η(5)-cyclopentadienyl(phenylvinylidene)(dicarbonyl)manganese → cymantrene (12079-65-1) + 2C5H5(1-)*4CO*2Mn(2+)*C6H5CHC(2-)=(C5H5)2(CO)4Mn2(CCHC6H5)

Conditions	Yield
With Pt(P(C6H5)3)4 In benzene a soln. of Mn-compd. (0.22 mmol) and Pt-compd. (0.20 mmol) in benzene was stirred under Ar at 20°C for 4 h;; evapn.; the residue was dissolved in hexane-benzene mixt. (2:1) and chromd. (alumina, hexane-benzene); removal of the solvent; residue was dissolved in ether; crystn. after cooling at -20°C;;	A n/a B 65%

dicarbonyl(η(5)-cyclopentadienyl)manganese(THF) + dichloromethane (75-09-2) + [(η5-cyclopentadienyl)2Mo2(μ-carbonyl)(μ-methoxycarbyne)(μ-dicyclohexylphosphide)] → cymantrene (12079-65-1) + [MnMo2(η5-cyclopentadienyl)3(μ3-methoxycarbyne)(μ-dicyclohexylphosphide)(μ-carbonyl)2(carbonyl)2]*1.5dichloromethane

Conditions	Yield
In toluene (N2, Schlenk technique); addn. of molybdenum compd. to THF soln. of manganese compd., dissolving in toluene, stirring at room temp. for 15 min; evapn., extn. (CH2Cl2/petroleum ether (1:7)), chromy. (alumina, CH2Cl2/petroleum ether 1:7, then 1:1) at 253 K, evapn., elem. anal.;	A n/a B 65%

(C5H5)MnOs3(H)(CHCHC6H5)(CO)12 → cymantrene (12079-65-1) + trans-(μ-H)Os3(CO)10(μ-η2-CHCH-phenyl) + H2Os3(HCCC6H5)(CO)9

Conditions	Yield
In pentane Ar atmosphere; stirring (20°C, 24 h); TLC (petroleum);	A n/a B 32% C 64%

triiron dodecarbonyl (17685-52-8) + [dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + p-Selenocresol (37773-23-2) → cymantrene (12079-65-1) + (μ-p-MeC6H4Se)2Fe2(CO)6 (172367-46-3, 350039-26-8) + C5H5Mn(CO)2Fe(CO)3CC6H5SeC6H4CH3 (349606-51-5)

Conditions

Yield

With N(CH2CH3)3 In tetrahydrofuran (N2); addn. of selenium compd. and amine to a soln. of iron carbonyl in THF, stirring at room temp. for 10 min, cooling to -100°C, pouring to manganese complex, warming to -80°C, stirring for 7-8 h at -80 to -45°C; evapn. at -50 to -40°C, column chromy (Al2O3, petroleum ether, petroleum ether/CH2Cl2 20:1, petroleum ether/CH2Cl2/Et2O 10:1:1), evapn., recrystn. (petroleum ether/CH2Cl2, -80°C); elem. anal.;

A 6% B 25% C 63%

[dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + tetramethylammonium hydridoirontetracarbonyl (63814-56-2) → cymantrene (12079-65-1) + [(C5H5)Mn(CO)2Fe(CHC6H5)(CO)3]

Conditions	Yield
In tetrahydrofuran (N2); addn. of the Mn complex at -90°C to the Fe compd. in THF with vigorous stirring, further stirring (-90 to -45°C, 4 h); evapn. to dryness (high vacuum, -45 to -40°C), chromy. (neutral alumina; light petroleum, then light petroleum/CH2Cl2; -25°C), collection, solvent removal (vac.), recrystn. (light petr. or light petr./CH2Cl2 at -80°C); elem. anal.;	A 25% B 63%

decacarbonyltriosmiumdihydride + η(5)-cyclopentadienyl(phenylvinylidene)(dicarbonyl)manganese → cymantrene (12079-65-1) + trans-(μ-H)Os3(CO)10(μ-η2-CHCH-phenyl) + 3Os*C2HC6H5*9CO = Os3(C2HC6H5)(CO)9 + (C5H5)MnOs3(H)(CHCHC6H5)(CO)12 + H2Os3(HCCC6H5)(CO)9

Conditions	Yield
In dichloromethane Ar atmosphere; stirring (20°C, 6 h); evapn. (vac.), extn. (CHCl3), chromy. (SiO2, petroleum ether, petroleumether/CHCl3 50:1, 5:1 and 2:1); elem anal.;	A n/a B 5% C 4.5% D 60% E 10%

diiron nonacarbonyl (15321-51-4) + η5-cyclopentadienyldicarbonyl(μ2-(phenyl)ethenylidene)bis(diphenylphosphinopropane)manganesepalladium → cymantrene (12079-65-1) + CpMnFe2(μ-3-C=CHPh)(CO)8 (208041-08-1) + (1,1,1,2,2,2-octacarbonyl)-[3-η2-bis(diphenylphosphino)propane-PP']-triangulo-diironpalladium(2Fe-Pd,Fe-Fe)

Conditions	Yield
In benzene under Ar; stirred at 70°C for 30 min; filtration (0.5 cm Al2O3), concn. in vac., chromy. (Al2O3, hexane-benzene), elem. anal.;	A n/a B 53% C 28% D >1

[(C5H5)Mn(CO)2Fe(CHC6H5)(CO)3] + carbon monoxide (201230-82-2) → cymantrene (12079-65-1) + [Fe(C6H5CHCO)(CO)3] (204716-14-3)

Conditions	Yield
In tetrahydrofuran (N2); bubbling CO gas through a soln. of the Mn-Fe complex in THF at -40to -10°C for 4 h; removal of solvent (vac.), chromy. (neutral alumina; light petroleum, then light petroleum/CH2Cl2), collection, removal of solvents (vac.), recrystn. (light petroleum or light petroleum/CH2Cl2; -80°C); elem. anal.;	A 31% B 46%

[dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + disodium tetracarbonylferrate → cymantrene (12079-65-1) + [MnFe(CO)5(C5H5)(C(COC2H5)C6H5)]

Conditions	Yield
In tetrahydrofuran (N2); addn. of the Mn complex to the Fe complex salt in THF with stirring at -90°C, further stirring (-90 to -80°C, 1 h, -60°C, 3 h); solvent removal (vac., -40°C), chromy. (-25°C, neutral alumina; light petroleum/CH2Cl2, then light petroleum/CH2Cl2/Et2O);	A 26% B 44%

silver(I) hexafluorophosphate (26042-63-7) + C5H5(CO)2MnSC6H4NO2 (136378-96-6) → cymantrene (12079-65-1) + {C5H5(CO)2Mn}2SC6H4NO2(1+)*PF6(1-)*0.5CH2Cl2 = {C5H5(CO)2Mn}2SC6H4NO2PF6*0.5CH2Cl2 (136379-20-9)

Conditions	Yield
In toluene carried out with exclusion of air and moisture; 1 equiv of AgPF6 added to a stirred soln. of the Pd complex; mixt. stirred for further 20 min. at room temp.; volume reduced in vac., pentane added, filtered through silanized silica gel, elution with CH2Cl2, crystn. from CH2Cl2-Et2O (1:1) at -30°C; elem. anal.;	A n/a B 42%

dicarbonyl(η(2)-hydroxypropyne)(η(5)-cyclopentadienyl)manganese → cymantrene (12079-65-1) + (η5-cyclopentadienyl)Mn(CO)2(=C=CHCH2OH)

Conditions	Yield
With hydrogenchloride; phenyllithium In diethyl ether byproducts: LiCl; Ar atmosphere; addn. of PhLi in ether to soln. of Mn-complex, stirring (-60°C, 30 min, at -20°C fo 30 min), acidification (HCl inether); sepn. of LiCl, filtration), evapn. (vac.), chrpmy. (5°C, ether/CH2Cl2 (1:4), ether);	A n/a B 40%

[dicarbonyl(π-cyclopentadienyl)(phenylcarbene)manganese]tetrabromoborate + (NEt4)2{(iron)2(carbonyl)8} → cymantrene (12079-65-1) + [MnFe(CO)5(C5H5)(C(COC2H5)C6H5)] + [((C5H5)Mn(CO)2CC6H5)2Fe2(CO)8]

Conditions	Yield
In tetrahydrofuran (N2); addn. of the Mn complex to the Fe complex salt in THF with stirring at -90°C, further stirring (-90 to -80°C, 1 h), warming to -50°C over 3 h; evapn. to dryness (high vac., -40°C), chromy. (-25°C, neutral alumina; light petroleum/CH2Cl2, then light petroleum/CH2Cl2/Et2O); elem. anal.;	A 23% B 39% C 19%

(η5-cyclopentadienyl)(η2-but-1-yn-3-ol)dicarbonylmanganese → cymantrene (12079-65-1) + (η5-cyclopentadienyl)(η2-but-1-en-3-one)dicarbonylmanganese

Conditions

Yield

With phenyllithium In diethyl ether byproducts: LiCl; addn. of 1 N soln. of C6H5Li in ether (4.06 mmol) to soln. of (C5H5)(OC)2Mn(CHCCH(CH3)OH) (4.06 mmol) in ether, stirring mixt. for 0.5 h at-60°C, 0.5 h at -20°C, acidifying with 1 N HCl in ether (dry solvents, Ar-atmosphere); filtering to remove LiCl, evapg. solvent in vac., chromy. of residue on SiO2-column (5°C), eluation with ether (elem. anal.);

A n/a B 35%

cymantrene (12079-65-1) + Me3SiNSO (7522-26-1) + water (7732-18-5) → π-C5H5Mn(CO)2(SO2)

Conditions

Yield

In tetrahydrofuran; acetone byproducts: Me3SiOH; Irradiation (UV/VIS); under Ar, soln. of Mn-complex was stirred for 4-5 h at -15 °C during irradn. with Hg-lamp., sulfinylimide was used in slight excess, soln. was warmed up to room temp. after 30 min, stirring for 2-3 h; soln. was evapd. in vac., subl., residue was dissolved in wet acetone, mixt. was stood for several days at room temp., elem. anal.; HNSO-complexwas not isolated, detected by spectr. methods;

99%

cymantrene (12079-65-1) + water (7732-18-5) + N-phenylsulfinylamine (222851-56-1) → π-C5H5Mn(CO)2(SO2)

Conditions

Yield

In tetrahydrofuran; acetone byproducts: PhNH2; Irradiation (UV/VIS); under Ar, soln. of Mn-complex was stirred for 4-5 h at -15 °C during irradn. with Hg-lamp., sulfinylimide was used in slight excess, soln. was warmed up to room temp. after 30 min, stirring for 2-3 h; soln. was evapd. in vac., subl., residue was dissolved in wet acetone, mixt. was stood for several days at room temp., elem. anal.;

99%

cymantrene (12079-65-1) → (acetylcyclopentadienyl)tricarbonylmanganese

Conditions	Yield
With CH3COCl; AlCl3 In dichloromethane byproducts: HCl; (Ar), to CH3COCl in CH2Cl2 added AlCl3 for 10 min, Mn-complex in CH2Cl2 added dropwise for 3 h; hydrolysed, HCl added, extracted, washed with H2O, dried over Na2SO4, filtered, solvent removed in vac.;	96%

cymantrene (12079-65-1) + Cyclohexyl isocyanide (931-53-3) → C5H5Mn(CO)2(CNC6H11)

Conditions	Yield
palladium(II) oxide In toluene byproducts: CO; (Ar); soln. of Mn complex and PdO was heated to reflux and the isonitrilederiv. was added, refluxing was continued for 6 h, react. was monitored by TLC; chromy. (Kieselgel, CH2Cl2/hexane); recrystn. from CH2Cl2/hexane; elem. anal.;	95%

cymantrene (12079-65-1) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → tricarbonyl(formylcyclopentadienyl)manganese

Conditions	Yield
Stage #1: cymantrene With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at -78 - 20℃; for 2h;	94.5%
With n-butyllithium; ammonium chloride In tetrahydrofuran; Petroleum ether byproducts: (CH3)2NH; Ar; soln. of (OC)3MnC5H4Li, prepd. at -50°C from soln. of (OC)3MnC5H5 and soln. of n-butyl lithium in THF, cooled to -70°C, addedin 2-5 min to DMF; mixt. stirred (1-1.5 h, -10 - -5°C); satd. soln. of NH4Cl in H2O added; aq. layer washed (ether); org. extract dried (MgSO4); solvent distilled off; residue chromd. (SiO2, 1/2 petroleum ether-benzene);	75%
With n-C4H9Li; NH4Cl In N,N-dimethyl-formamide (Ar); treatment soln. of cymantrene/THF with n-BuLi/C6H14 at -50°C for 15 min, cooling, transferring into Schlenk tube with DMF; stirringat 0°C for 90 min, addn. of soln. of NH4Cl; Bull. SSSR Acad. of Sci., Div. of Chemistry 29 (1990)2387;	72%

cymantrene (12079-65-1) + C5H5(PMe3)Co{μ-CO}{μ-CS}Mn(CO)C5H5 → C5H5Co(P(CH3)3)(CO)(CS(Mn(CO)2(C5H5)))Mn(CO)C5H5

Conditions	Yield
With THF In tetrahydrofuran byproducts: CO; Irradiation (UV/VIS); irradn. until end of gas-evolution, 24 h stirred at 25°C, addn. of further C5H5Mn(CO)2(THF), stirred 24 h at 25°C.; recrystn. from THF-hexane; elem. anal.;	94%

cymantrene (12079-65-1) + trimethyl(methylene)phosphorane (14580-91-7, 29218-61-9) → tetramethylphosponium-{dicarbonyl(η5-cyclopentadienyl)-{η1-2-(trimethylphosphoranylidene)acetyl}manganate(1-)}

Conditions	Yield
In pentane stirred at 25°C for 20 min; cooling at 0°C, ppt. washed with ice-cold pentane, dried at 25°C, elem. anal.;	93%

Methyltrichlorosilane (75-79-6) + cymantrene (12079-65-1) → tris(η5-cyclopentadienyl(tricarbonyl)manganese)methylsilane (114835-71-1)

Conditions	Yield
With s-BuLi In tetrahydrofuran; cyclohexane To a soln. of Fe-compd. in THF a soln. of s-BuLi is added at -78°C, mixt. is stirred for 20 min. CH3SiCl3 is added dropwise via a syringe at -78°C, mixt. is allowed to warm to 20°C (N2).; Solvent is removed in vac., residue is chromd on alumina III, elem. anal.;	93%

cymantrene (12079-65-1) + boron tribromide (10294-33-4) → 1,3-bis(dibromoboryl)cymantrene (1010720-67-8)

Conditions	Yield
In neat (no solvent) byproducts: HBr; under N2; cymantrene dissolved in neat BBr3; refluxed for 44 h; HBr condensed into cold trap (liq. N2); react. mixt. cooled to room temp.; filtered; filtrate evapd. slowly in vac.; detd. by X-ray powder diffraction;	93%

cymantrene (12079-65-1) → hexacarbonyl(μ,η5:η5-fulvalene)dimanganese

Conditions	Yield
With n-butyl lithium; copper(II) chloride In diethyl ether; hexane ether soln. of CpMn(CO)3 was treated with hexane soln. of n-BuLi at -70°C in anaerobic conditions, stirred for 1 h at this temp., anhyd. CuCl2 was added, suspn. was stirred for 3 h at -60°C and brought to room temp. within 5 h; hydrolyzed (H2O), ether phase dried, evapd., residue was sublimed at 110°C under high vac.; elem. anal.;	92%

8-bromoquinoline (16567-18-3) + cymantrene (12079-65-1) → tricarbonyl[η5-(8-quinolyl)cyclopentadienyl]manganese(I) (342813-38-1)

Conditions

Yield

With n-butyllithium; ZnCl2; bis(triphenylphosphine)palladium(0) In tetrahydrofuran byproducts: LiCl; 1.) n-BuLi in hexane (-78°C), stirred for 1 h; 2.) ZnCl2 in THF, stirred for 1 h; 3.) Pd(PPh3)2, 8-bromoquinoline were added dropwise, the soln. was allowed to warm to room temp., stirred for 5 d (Ar, protection against light); aq. NaOH was added, stirred for 1.5 h, the organic layer was sepd., extd. with THF, dried (MgSO4), filtered, evapd., chromy. on Al2O3/5% H2O with toluene, elem. anal.;

92%

cymantrene (12079-65-1) + propionyl chloride (79-03-8) → (Propionylcyclopentadienyl)tricarbonylmanganese (62010-78-0)

Conditions	Yield
aluminium trichloride In carbon disulfide (Ar); Schlenk tube; AlCl3 was added to soln. of cymantrene and propionylchloride in CS2; after 1.5 h CS2 was removed in vac.; water was added at 0°C; extd. (Et2O); dried (MgSO4); soln. concd.; pentane added; recrystd. (Et2O/pentane); elem. anal.;	92%
With AlCl3 In carbon disulfide (Ar); addn. of AlCl3 to a soln. of manganese complex in CS2, addn. of a soln. of propionyl chloride in CS2, stirring for 1.5 h; evapn., addn. of water at 0°C, extn. with Et2O, drying (MgSO4), concn., addn. of pentane, recrystn. (ether/ pentane); elem. anal.;	92%
With aluminum (III) chloride In dichloromethane at 20℃; for 4h; Schlenk technique;	71%

hexafluorophosphoric acid + cymantrene (12079-65-1) + buta-1,3-diene (106-99-0) → syn-{(η5-cyclopentadienyl)manganese(dicarbonyl)(η3-H(CH3)CCHCH2)}(PF6)

Conditions	Yield
In diethyl ether; water Irradiation (UV/VIS); N2 atmosphere; addn. of org. comp. and aq. soln. of HPF6 to soln. of Mn-compd. in Et2O, purging with N2, stirring, irradiation without stirring (15-25°C, 15-30 min, 365 nm); 22% conversion; filtn., washing (ether), precipitaion from acetone/ether (0°C); elem. anal.;	91%

n-butyllithium (109-72-8, 29786-93-4) + cymantrene (12079-65-1) + tungsten hexacarbonyl (14040-11-0) + N,N,N,N,-tetramethylethylenediamine (110-18-9) + trifluoroacetic anhydride (407-25-0) → {WMn(μ-σ:η5-CC5H4)(CO)5(N,N,N',N'-tetramethylethylenediamine)(O2CCF3)}

Conditions

Yield

In tetrahydrofuran; diethyl ether; hexane treating 31 mmol (Mn(CO)3(C5H5)) in THF/ ether at -80°C with 32.0 mmol LiC4H9 in hexane; stirring for 1 h; addn. of 31.3 mmol (W(CO)6); stirring at -10°C for 1 h; cooling to -80°C; treating with (CF3CO)2O in THF; addn. of ligand;; warming to room temperature; evaporation under reduced pressure; extraction with dichloromethane; chromy. (CH2Cl2); concn. in vac.; diln. with petroleum; cooling to -80°C; pptn.; decantation; washing with petroleum; drying in vac.; elem. anal.;;

91%

oxirane (75-21-8) + cymantrene (12079-65-1) + p-toluenesulfonyl chloride (98-59-9) → (η(5)-C5H4CH2CH2OSO2C6H4CH3)Mn(CO)3 (215460-58-5)

Conditions

Yield

With n-butyllithium In tetrahydrofuran; pentane byproducts: LiCl; N2-atmosphere; addn. of equimolar amt. of BuLi (in pentane) to Mn-complex soln. (in THF) at -78°C, addn. of slight excess of ethylene oxide (after 3 h, -78°C), warming to 0°C (after 2 h), addn. of equimolar amt. of tosyl chloride; solvent removal (after 30 min, 25°C, vac.), extn. into CH2Cl2, filtration off of LiCl (Celite), evapn., chromy. (SiO2, CH2Cl2); elem. anal.;

91%

oxirane (75-21-8) + cymantrene (12079-65-1) → C10H9MnO4

Conditions	Yield
Stage #1: cymantrene With n-butyllithium In tetrahydrofuran; hexane at -80℃; for 1.5h; Schlenk technique; Inert atmosphere; Stage #2: oxirane In tetrahydrofuran; hexane at -80 - 25℃; Schlenk technique; Inert atmosphere; Stage #3: With water In tetrahydrofuran; hexane at 25℃; Schlenk technique; Inert atmosphere;	91%

cymantrene (12079-65-1) + ethene (74-85-1) → (η5-C5H5)Mn(CO)2(η2-C2H4) (12108-31-5)

Conditions	Yield
In further solvent(s) Irradiation (UV/VIS); cymantrene soln. in subcritical and supercritical ethylene (-40 - 50°C, 35-2600 bar), photolysis (10 h); not isolated;	90%

tetrahydrofuran (109-99-9) + cymantrene (12079-65-1) + tetracarbonylbis(η5-cyclopentadienyl)-μ4-diarsenic-dimolybdenum (Mo-Mo) (83025-09-6) → tetracarbonylbis(η5-cyclopentadienyl)μ4-diarsenic-bis{dicarbonyl(η5-cyclopentadienyl)manganese}dimolybdenum (Mo-Mo) (111769-92-7) + carbon monoxide (201230-82-2)

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); 4.90 mmol (C5H5)Mn(CO)3 in THF photolyzed for 90 min; soln. concd. and added to 4.28 mmol (C5H5)2Mo2(CO)4As2; soln. stirred for 6 h at room temp.; solvent concd.; chromy. (silica gel) with hexane yields (C5H5)Mn(CO)3, then with toluene/ether (1:1) (CpMo(CO)2)2(CpMn(CO)2As)2 which is crystd. from CH2Cl2/hexane at -18°C; elem. anal.;	A 90% B n/a

cymantrene (12079-65-1) + (η5-C5H4(COPh))Re(CO)3 (12267-07-1) → (η5-cymantrenylphenylhydroxymethylcyclopentadienyl)tricarbonylrhenium

Conditions

Yield

With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane cymantrenyllithium prepd. above -78°C from cymantrene, TMEDA, and n-BuLi; after 45 min, the Re complex is added; mixt. warmed to room temp. for 20 h; hydrolyzed; washed with distilled water; solvent removed under high vac.; chromy on silica with dichloromethane/hexane eluent; recrystd. from ethanol/water; elem. anal.;

90%

cymantrene (12079-65-1) + methyl isocyanate (593-75-9, 685498-28-6) → Mn(η-cyclopentadienyl)(CO)2(methyl isocyanide)

Conditions	Yield
In tetrahydrofuran byproducts: CO; Irradiation (UV/VIS); N2-atmosphere; equimolar amts.or excess MeNC, 100-W Hg lamp (18 h); evapn., chromy. (Al2O3), evapn., crystn. (-78°C, petroleum ether); elem. anal.; yield related to equimolar amts. of educts;	90%
palladium(II) oxide In toluene byproducts: CO; (Ar); soln. of Mn complex and PdO was heated to reflux and the isonitrilederiv. was added, refluxing was continued for 24 h, react. was monitored by TLC; chromy. (Kieselgel, CH2Cl2/hexane); recrystn. from CH2Cl2/hexane; elem. anal.;	5%

cymantrene (12079-65-1) + [2,6-diphenylpyrylium](PF6) (171562-97-3) + trityl tetrafluoroborate (341-02-6) → [(4-cyclopentadienyl-2,6-diphenylpyrylium)Mn(CO)3](BF4) (158840-67-6)

Conditions	Yield
With BuLi In tetrahydrofuran; diethyl ether; hexane N2-atmosphere; addn. of BuLi (hexane) to THF soln. of Mn-complex at -60°C, stirring for 1 h, addn. of pyrylium (THF:ether), warming to 0°C, addn. of aq. NH4Cl, extn. (ether), drying (MgSO4), chromy. (Al2O3, pentane), addn. of MeCN; addn. of Ph3CBF4, stirring for 30 min, addn. of ether, collection (filtration); elem. anal.;	89%

cymantrene (12079-65-1) + 2-chloropropionyl chloride (625-36-5) → (3-chloropropionyl)-cymantrene

Conditions	Yield
With aluminum (III) chloride In dichloromethane at 20℃; for 5h; Friedel-Crafts Acylation; Schlenk technique;	88%

cymantrene (12079-65-1) + chloro-diphenylphosphine (1079-66-9) → tricarbonyl(η5-diphenylphosphinocyclopentadienyl)manganese (62980-80-7)

Conditions	Yield
With n-butyllithium In not given byproducts: LiCl; Complex was treated with n-BuLi at -70°C, PPh2Cl was added, the mixt. was kept at room temp. for 2 h;; aq. HCl was added with cooling, aq. NaOH was added to pH 8, extd. with ether or CH2Cl2, the organic layer was washed with water, evapd., crystd. from hexane or EtOH; elem. anal.;;	87.4%

cymantrene (12079-65-1) + (η5-cyclopentadienyl)(η2-selenoformaldehyde)(trimethylphosphine)rhodium(I) → (η5-cyclopentadienyl)(trimethylphosphine)rhodium(μ-η1,η2-selenoformaldehyde)(dicarbonyl(η5-cyclopentadienyl)manganese)

Conditions	Yield
In tetrahydrofuran byproducts: CO; Irradiation (UV/VIS); irradiating a soln. of Mn(CO)3(C2H5) until the CO evolution beeing finished (ca 2 - 3 h), adding the Rh complex, stirring (ca 24 h, room temp.); concg., chromy. (Al2O3, benzene), recrystn. (pentane);	87%
In tetrahydrofuran byproducts: CO; Irradiation (UV/VIS); N2 atmosphere; photolysis of Mn-complex in THF (Hg-vapor lamp, 2-3 h), addn. of Rh-complex, stirring (room temp., 24 h); solvent removal, extraction (benzene), concn., chromy. (Al2O3, benzene/pentane 1:1), evapn. (vac.), crystn. (pentane, -78°C), collection (filtn.), washing (pentane), drying (vac.); elem. anal.;	87%

cymantrene (12079-65-1) + trisodium tris(3-sulfophenyl)phosphine (63995-70-0) + tris(natrium-m-sulfonatophenyl)phosphanoxid (98511-67-2) → (η5-cyclopentadienyl)carbonylbis{tris(sodium-m-sulphonatophenyl)phosphine}manganese-hexahydrate + (η5-cyclopentadienyl)dicarbonyl{tris(sodium-m-sulphonatophenyl)phosphine}manganese-trihydrate

Conditions	Yield
In tetrahydrofuran; water byproducts: CO; Irradiation (UV/VIS); (N2 or Ar); irradiation of soln. of Mn-complex in THF (high pressure Hg-lamp, 90 min, 15°C), addn. to org. compd. in H2O, stirring (16 h); phase sepn., washing org. phase (H2O), aq. phase (n-pentane), evapn. (vac.), chromy. (Sephadex), chromy. (Fractogel, H2O/EtOH); elem. anal.;	A 87% B 25%

Upstream product

• 14516-54-2 bromopentacarbonylmanganese(I) 
• 17685-52-8 triiron dodecarbonyl 
• 109-79-5 n-butanethiol 
• 121-44-8 triethylamine 
• 7439-96-5 manganese 
• 542-92-7 cyclopenta-1,3-diene 
• 66034-78-4 pentacarbonyl(perchlorato)manganese 
• 504-64-3 carbon suboxide 
• 14221-01-3 tetrakis(triphenylphosphine) palladium⁽⁰⁾ 
• 943233-68-9 ((CH₃)3C₆H₂)2C₂N₂H₂PC₅H₅ 
• 73138-26-8 manganocene 
• 14024-00-1 vanadium hexacarbonyl 
• 201230-82-2 carbon monoxide 
• 26042-63-7 silver(I) hexafluorophosphate 

Downstream Products

• 7439-96-5 manganese 
• 244264-89-9 (η5-C5H5)Mn(CO)2(H2O) 
• 12119-78-7 (C₅H₅)(CO)2Mn(P(C₆H₅)2CH₂CH₂P(C₆H₅)2)Mn(CO)2(C₅H₅) 
• 114095-82-8 dicarbonyl(cyclopentadienyl)phenylthiomanganese 
• 55971-21-6 dicarbonyl(η5-cyclopentadienyl)(diphenylcarbene)manganese 

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Solid-phase microextraction combined with gas chromatography and atomic emission detection for the determination of CYCLOPENTADIENYLMANGANESE TRICARBONYL (cas 12079-65-1) and (methylcyclopentadienyl)manganese tricarbonyl in soils and seawaters07/29/2019

A method based on solid-phase microextraction with capillary gas chromatography and microwave-induced plasma atomic emission detection (SPME-GC-MIP-AED) for the determination of cyclopentadienylmanganese tricarbonyl (CMT) and its methyl derivative, (methylcyclopentadienyl)manganese tricarbonyl (...detailed

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