The Chemistry of Cyclopentadienylmanganese Tricarbonyl Compounds. I. Acylation and Alkylation<sup>1</sup>

Kozikowski, John; Maginn, R. E.; Klove, Marcella Sizen

doi:10.1021/ja01521a019

Cited by 44 publications

(8 citation statements)

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“…The acidity and basicity values obtained experimentally from the half-neutralization potentials for phenol 16 and amine 17 were not conveniently comparable to literature pK values obtained under aqueous conditions. To make them comparable, it was necessary to adjust the values on the basis of a standard phenol (phenol was chosen) and a standard amine (aniline was chosen) which were run under analogous conditions.…”

Section: Methodscontrasting

confidence: 81%

“…(?r~Aminocyclopentadienyl)tetraphenylcyclobutadienecobalt (17) .-(v -Phthalimidocyclopentadienyl)tetraphenylcyclobutadienecobalt (0.02 g, 0.03 mmol), 3 ml of 95% hydrazine in 1 ml of water, and 5 ml of ethanol were combined in a 50-ml flask equipped with a condenser. The suspension was refluxed until all the solid was dissolved and then poured into cold water.…”

Section: Methodsmentioning

confidence: 99%

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Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Rausch¹,

Genetti²

1970

J. Org. Chem.

247

122

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The reaction of -cyclopentadienyldicarbonylcobalt and diphenylacetylene in refluxing xylene products ircyclopentadienyltetraphenylcyclobutadienecobalt (1) and ?r-cyclopentadienyltetraphenylcycIopentadienonecobalt (2) in yields of 50 and 10%, respectively. This method has also been extended to the direct synthesis of the corresponding trimethylsilyl (3, 5) and phenyl (4, 6) derivatives, starting with trimethylsilylor phenylcyclopentadiene. The 7r-cyclopentadienyl ring in 1, as in ferrocene, undergoes a number of electrophilic ring substitution reactions. Acetoxymercuration with a perchloric acid catalyst, followed by treatment with lithium chloride, produces a chloromercuri derivative 7 in 65% yield, together with a l,2-bis(chloromercuri) derivative 8. Complex 7 is readily converted into its iodo analog 9. The transmetalation of 7 with n-butyllithium gives a lithium intermediate 10 which on treatment with acetyl chloride affords the acetyl derivative 11. When 9 is heated with copper-bronze or with cuprous cyanide in A-methyl-2-pyrrolidone, the Ullmann product 12 and the cyano derivative 13 are obtained. Similar reactions with cupric acetate and cupric phthalimide produce acetate 14 and phthalimido IS derivatives, respectively, which on hydrolysis give phenol 16 and amine 17. The relative acidity and basicity of these products have been determined. Aminomethylation and Vilsmeier formylation give dimethylaminomethyl (18) and formyl (20) derivatives in yields of 74 and 8%, respectively. The conclusion is drawn that•, while 1 participates in a variety of electrophilic substitution reactions, if is in general less reactive than is ferrocene.Although the concept of aromaticity is still not well defined, ferrocene and related organometallic compounds are generally considered "aromatic" in that they resist ring-addition reactions and undergo ring-substitution reactions. Thus, ferrocene is known to undergo various electrophilic substitution reactions such as Friedel-Crafts acylation,2 alkylation,3•4 formylation,6-7 sulfonation,8-10 acetoxymercuration,11•12 and aminomethylation.13 Following these initial studies on ferrocene, various other organotransition metal compounds containing a -cy clopentadieny 1 ring were found to exhibit similar chemical reactivities. Thus, ruthenocene,14 osmocene,14 cymantreñe,15-18 and its technitium19 and rhenium19•20 analogs, -cyclopentadienyltetracarbonylvanadium,21•22 and -cyclopenta-(1) Alexander von Humboldt Research Fellow, 1969-1970

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Section: Methodscontrasting

confidence: 81%

Section: Methodsmentioning

confidence: 99%

Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Rausch¹,

Genetti²

1970

J. Org. Chem.

247

122

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“…Total dehydration of 15 or 14 to give 15, R=Ph 17, R = Ph 14, R= Me 18, R = Me 17 or 18, respectively, could be carried out by simply chromatographing the alcohols on activated silica gel. A more reliable synthesis of (t/Msopropenylcyclopentadienyl)dicarbonylnitrosylchromium (18) was developed which involved the acid-catalyzed dehydration of 14 in refluxing benzene using p-toluenesulfonic acid in the presence of hydroquinone as a radical inhibitor (eq 8). Another reaction typical of stabilized carbonium ion intermediates is the hydrogenolysis of alcohols and ketones with lithium aluminum hydride and aluminum chloride.40 Treatment of 6, 12, or 13 with 1:1 lithium aluminum hydride-aluminum chloride led to products of hydrogenolysis in 55-65% yield (eq 9 and 10).…”

Section: Resultsmentioning

confidence: 99%

Formation and reactions of ring-substituted derivatives of (.eta.5-cyclopentadienyl)dicarbonylnitrosylchromium

Rausch¹,

Mintz²,

Macomber³

1980

J. Org. Chem.

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“…TLC plates (20x20 cm, Silica gel 60 F254) were purchased from Merck. [(CO) 3 Mn(η 5 ‐C 5 H 4 COCH 3 )], [H 2 NN(H) C (O)R], (R = Rhodamine‐6G, Rhodamine‐B) were prepared following reported procedures …”

Section: Experimental Sectionsmentioning

confidence: 99%

Half sandwich based rhodamine ‐ hydrazone single molecule probe: Light responsive, metal sensing and imaging properties

Dewangan

Barik

Mishra

et al. 2018

Applied Organom Chemis

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Functionalization of cymantrenyl hydrazone system with rhodamine based fluorescent tag led to the formation of a significant molecule containing both, a half sandwich and a rhodamine fragments, [(CO) (2)), with selective metal ion sensing, light responsive and molecular switching behavior. The molecule (1) was structurally characterized by single crystal X-ray diffraction study. We have also explored Hg 2+ recognition and photosensing properties of compound 1 within a bacterial strain and THP-1 cancer cell lines to understand their potential in applications related to bioimaging, uptake and bioremediation activities. The study showed some significant intracellular metal recognition and imaging characteristics at different metal concentration.

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The Chemistry of Cyclopentadienylmanganese Tricarbonyl Compounds. I. Acylation and Alkylation¹

Cited by 44 publications

References 0 publications

Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Formation and reactions of ring-substituted derivatives of (.eta.5-cyclopentadienyl)dicarbonylnitrosylchromium

Half sandwich based rhodamine ‐ hydrazone single molecule probe: Light responsive, metal sensing and imaging properties

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The Chemistry of Cyclopentadienylmanganese Tricarbonyl Compounds. I. Acylation and Alkylation1

Cited by 44 publications

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Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Organometallic .pi. complexes. XXII. Chemistry of .pi.-cyclopentadienyltetraphenylcyclobutadienecobalt and related compounds

Formation and reactions of ring-substituted derivatives of (.eta.5-cyclopentadienyl)dicarbonylnitrosylchromium

Half sandwich based rhodamine ‐ hydrazone single molecule probe: Light responsive, metal sensing and imaging properties

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The Chemistry of Cyclopentadienylmanganese Tricarbonyl Compounds. I. Acylation and Alkylation¹