Investigation of Absorption Spectra of Bis(alkylxanthato)-platinum(Ⅱ) Complexs

Being widely used as good ligands,xanthates and related compounds have been extensively investigated.However,reports on Pt(Ⅱ) xanthates have been sparse so far.Watt et al.reported the synthesis and characterization of Pt(S_2COR)_2(R=Me,Et),but did not provide any absorption spectra of these complexes.We prepared twelve platinum (Ⅱ) xanthate complexes and examined their absorption spectra in detail.     

Reactivity of Geometric Isomers of (–)-Dichloropyridine(methyl-para-tolylsulfoxide)platinum(II) by Optical Rotatory Dispersion

The reactions of the optically active geometric isomers of the platinum(II) complex (–)-[Pt(Me-p-TolSO)(Py)Cl₂] with several nucleophilic reagents (Py, Ph₃PS, Ph₃P, Ph₃As, and Me₂SO) were studied by optical rotatory dispersion, IR spectroscopy, and ¹H and ³¹P NMR spectroscopy. A mechanism for the reaction is proposed.     

Synthesis of (±)-Bimatoprost

A general synthetic approach has been developed for the synthesis of a key intermediate (6) that can be elaborated into several ophthalmic prostaglandins and their derivatives. Using these strategy, we have obtained (±)-bimatoprost (1) and its analog, (±)-homobimatoprost (5).     

Cyclic structure of the β(γ)-hydroxy-(mercapto)alkylimines of aldoses

In solutions in DMSO-d₆, the products from the condensation of ethanolamine and 1,2- and 1,3-aminopropanols with aldoses are mixtures of the - and -pyranose forms, whereas the -mercaptoethylimines of aldoses have the 1,3-thiazolidine structure. Glucose -mercaptoethylimine is characterized by ring-chain tautomerism involving the -pyranose and diastereomeric 1,3-thiazolidine tautomers.Military-Medical Academy, St. Petersburg, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1068–1071, August, 1998.     

Electrochemistry of microparticles of tris (2,2′-bipyridine) ruthenium(II) hexafluorophosphate

The electrochemical behaviour of tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate (Ru(II)) microparticles, immobilised on a graphite electrode and adjacent to an aqueous electrolyte solution, has been studied by cyclic voltammetry and an in situ spectroelectrochemical technique. The solid Ru(II) complex exhibits one reversible redox couple with a formal potential (E_f) of 1.1 V versus Ag¦AgCl. The continuous cyclic voltammetric experiments showed that the Ru(II) microparticles are stable during the electrochemical conversions. The in situ spectroelectrochemical study showed that the absorbance at 463 nm decreased due to the oxidation of Ru(II) to Ru(III). Upon reduction, the growth of absorbance at 463 nm was observed due to the formation of Ru(II) complex and this process was reversible.     

Kinetics and mechanism of the anation of (αβ)-hydroxo(tetraethylenepentamine)cobalt(III) by thiosulfate, the base hydrolysis of the (sulfur-bonded) thiosulfato(tetraethylenepentamine)-cobalt(III) and photochemistry of oxygen and sulfur-bonded thiosulfato complexes

Summary The reaction of ()-(tetren)CoOH²⁺ with S₂O ₃ ^2- in the 7.25–8.28 pH range at 20–40 °C yielded S- (yellow) and O- (purple) bonded thiosulfato(tetren)cobalt(III) complexes, the former in larger quantities. The rate determining step is preceded by diffusion-controlled ion-pair [(tetren)CoOH²⁺,S₂O ₃ ^2- ] formation. Replacement of coordinated OH^- by S₂O ₃ ^2- is interpreted in terms of an internal conjugate base mechanism: (tetren)CoOH²⁺ (tetren-H)CoOH ₂ ²⁺ , the reactive amido conjugate base being generated by intramolecular proton transfer from the coordinated NH site.In acid medium the S-bonded (tetren)Co(S₂O₃)⁺ is highly stable to redox decomposition, in contrast to its pentaammine analogue. The complex however, undergoes base hydrolysis yielding the corresponding hydroxo complex. The rate and activation parameters for the base hydrolysis have been reported. Photolysis of O- and S-bonded isomers of [(tetren)CoS₂O₃]⁺ in acidic medium at 254 and 313 nm, respectively, yielded aquation products accompanied by some decomposition of S₂O ₃ ^2- .     

Synthesis of (±) Combretastatin

Combretastatin (1) is a new plant product isolated recently by Pettit et al ¹. from the South African tree, Combretum caffrum that possesses central nervous system antineoplastic activity and is being evaluated against several of National Cancer Institute's key evaluation systems. The structure of 1 was established on the basis of its spectral properties and confirmed by X-ray analysis. However, the absolute configuration and the synthesis of 1 have not been reported so far. As combretastatin is present in the plant in only 0.0008% and the isolation technique is much tedious, there is an urgent need for the synthesis of 1 for further evaluation of its activity. This prompted us t o report the first synthesis of (±)1.     

Electrochemical Behavior of Novel Bis(β-diketonate)phthalocyanine Complexes of Zr(IV) and Hf(IV)

We have used cyclic voltammetry to study the electrochemical properties of novel bis(-diketonate)phthalocyanine complexes of Zr(IV) and Hf(IV) in dichloromethane. We found three waves for the studied complexes that can be attributed to one-electron processes MPc(L)^0/1– ₂, MPc(L)^1+/0 ₂ and MPc(L)^2+/1+ ₂. We have shown that the electrochemical behavior of the complexes depends on the nature of the substituents in axial ligands and does not depend on the nature of the metals. We have analyzed the stability of the one-electron oxidation products of the complexes relative to disproportionation.     

Study of Intramolecular Cyclization of N-styryl-oxo-cinnamides (Ⅱ)

lnthepreviouspaper',wereportedtheintramolecularcyclizationsofamide4anditscis-eneisomerinanattempttosynthesizehomoclausenamideandzetaclausenamide2.Inordertostudytherelationshipbetweenthestereochemistryandtheilltramolecularcyclizationofthisseriesofcompounds,theamides5(cis-oxirane,trans-ene)and8(cis-oxirane,cis-ene)wereprepared,andtheirintramolecularcyclizationswerereportedinthispaper.Theamide5withm.p.152.O-l54.O"CwasobtainedfromDarzen'scondensationofcompound3withPhCHOinMeOHatl5-2OoCwithMeO…     

Crystal Structures of Cu(Ⅰ) and Cu(Ⅱ) Complexes of Tris(N-n-propylbenzimidazol-2-ylmethyl)amine

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｃｏｎｔｒｏｌｅｄｄｅｓｉｇｎｏｆｓｏｌｉｄ－ｓｔａｔｅａｒｃｈｉｔｅｃｔｕｒｅｓａｎｄｃｒｙｓｔａｌｅｎｇｉｎｅｅｒｉｎｇｈａｓｃｕｒｒｅｎｔｌｙｂｅｅｎｒｅｃｏｇｎｉｚｅｄａｓｏｎｅｏｆｔｈｅｍｏｓｔｉｍｐｏｒｔａｎ...     

Determinations of combustion and formation enthalpies of C_(60)and C_(70)

Ｆｕｌｌｅｒｅｎｅｓａｒｅａｋｉｎｄｏｆｃａｒｂｏｎａｌｌｏｔｒｏｐｅｓｆｏｕｎｄｒｅｃｅｎｔｌｙ,ａｎｄｈａｖｅｄｉｓｔｉｎｃｔｉｖｅｓｔｒｕｃｔｕｒｅｓａｎｄｐｒｏｐｅｒｔｉｅｓ.Ｆｏｒｅｘａｍｐｌｅ,Ｃ60ｈａｓａｆｏｏｔｂａｌｌｌｉｋｅｃａｒｂｏｎｓｋｅｌｅｔｏｎｗｉｔｈ20ｓｉｘｍｅｍｂｅｒｅｄｒｉｎｇｓ,12ｆｉｖｅｍｅｍｂｅｒｅｄｒｉｎｇｓａｎｄａｌａｒｇｅｂａｌｌｓｈｅｌｌｌｉｋｅπｂｏｎｄｓｙｓｔｅｍ.Ａｌｔｅｒｎａｔｉｖｅｌｙ,Ｃ70ｈａｓａｎｅｌｌｉｐｓｏｉｄｌｉｋｅｃａｒｂｏｎｓｋｅｌ…     

Laser flash photolysis of fullerols of C_(60) and of C_(70) in aqueous solutions

Ｓｉｎｃｅｇｒａｍｑｕａｎｔｉｔｉｅｓｏｆｆｕｌｌｅｒｅｎｅｓｗｅｒｅｓｅｐａｒａｔｅｄｆｒｏｍｃａｒｂｏｎｓｏｏｔｓ,ｍａｎｙｓｔｕｄｉｅｓｈａｖｅｂｅｅｎｔｒｉｇｇｅｒｅｄｏｎｔｈｅｉｒｓｔｒｕｃｔｕｒｅｓ,ｐｒｏｐｅｒｔｉｅｓａｎｄｒｅａｃｔｉｏｎｓ.Ａｓｆｕｌｌｅｒｅｎｅｓｃａｎｐｒｏｄｕｃｅｖｅｒｙｈｉｇｈｑｕａｎｔｕｍｙｉｅｌｄｓｏｆｓｉｎｇｌｅｔｏｘｙｇｅｎｗｈｉｌｅｅｘｃｉｔｅｄｂｙｌｉｇｈｔ,ｍｏｒｅｉｎｔｅｒｅｓｔｈａｓｂｅｅｎｆｏｃｕｓｅｄｏｎｔｈｅｅｘａｍｉｎａｔｉｏｎｏｆｔ…     

Concept of Superbasicity of 1,8-Bis(dialkylamino)naphthalenes (“Proton Sponges”)

Superbasic properties of naphthalene protone sponges are determined by the p character of the unshared electron pair on the nitrogen atom of the dialkylamino group and by distortion of the n,* conjugation.     

Theoretical Investigations of the Inclusion Processes of (4-tert-butylphenyl) (3-sulfonatophenyl) (phenyl) Phosphine in β-Cyclodextrin

Quantum mechanical calculations on the (4-tert-butylphenyl)(3-sulfonatophenyl) (phenyl) phosphine/-cyclodextrin inclusion complex werecarried out using semi-empirical calculations. Inclusion process pathways are describedand the most probable structures of the 1:1 complex are sought through a global potentialenergy scan. The calculations suggest that the most stable structure is obtained whenthe aromatic ring bearing the tert-butyl group is includedinto the hydrophobic cavity of the -cyclodextrin from theside of the primary hydroxyl groups.     

Synthesis and Magnetic Properties of Fe(II) and Nd(III) Complexes of Poly(N-2-thiazolylacrylamide)

In recent years,the organic ferromagnets have drawn growing attention due to their characteristics of structural diversities,low density,and readily processing1-3.Design and synthesis of magnetic polymers are one of great challenges in today′s magnetic material research,and some significant achievements have been made in this field4,5.In this article,we describe the synthesis of acrylamide-type polymer with pendent thiazolyl groups(Scheme1).The as-prepared polymer exhibited better solubility …     

Crystal Structure of N-(O-Ethylphenylthionophos-phonyl) N'-(O-p-iodinephenylphenylthionophos-phonyl)thiosemicarbazide

1mThODUCT'ONSomecomPOundsofN--thionophosphonylandN,N'--his(thionophosphonyl)thiOSemicarbazideshaveattractedmuchattentionandbeenextensivelystudiedinrecentyears"~'i.ThiskindofcomPOundsareknowntohaveobviousantibacterialandantifungalactivitiest3}.TherearetwochiralphosphoratomsinthecomPOundsofN,N'--his(thionophosphonyl)thiosemicarbazide.Inordertostudyfurthertherelationshipbetweenthestructureandbiologicalactivities,hereinwerePOrtthecrystalstructureofakindofN,N'--his(thionophosphonyl)thiose…     

Total Synthesis of (±)-Boschnialactone and (±)-Tetrahydroanhydrodesoxyaucubigenin

A total synthesis of (±)-boschnialactone ( 1 ) and (±)-tertahydroanhydrodesoxyaucubigenin ( 2 ) is described and trisubstitued cyclopentenoid 3 is a key intermediate.     

Crystal Structure of cis-Dichlorobis-(1,10-phenanthroline) Manganese(Ⅱ)

1INTRODUCTIONRecently,considerableattentionhasbeenpaidtotheinvestigationofcoordinationchemistryofmanganeseindifferentoxidationstatesnotonlybecauseofthediscoveryoftightlyboundmanganeseatomsinvariousbiomolecules[libutalsobecauseoftheirinterestingstructural,magneticandspectroscopicfeatures.Wehavepreparedseveralcomplexesofmanganese(n)withdifferentligands.Thestructuresandfeaturesofthesecompoundsarestudiedsystematically.Inthispaperwedescribethestructureofthecomplexwiththeligandsofphenanthroline…     

Total synthesis of (±)-maistemonine and (±)-stemonamide

The first total synthesis of polycyclic Stemona alkaloid maistemonine has been achieved. The efficient approach features a stereoselective intramolecular Schmidt reaction, a ketone-ester condensation, and a Reformatsky reaction. Additionally, another Stemona alkaloid stemonamide was divergently synthesized from a common intermediate.     

Enantiospecific Synthesis of (–)-Cuspareine and (–)-Galipinine

An enantiospecific route to the synthesis of tetrahydroquinoline alkaloids (–)-cuspareine and (–)-galipinine is reported. Coupling of an iodide derivative of D-serine with aromatic dithianes and Pd-catalyzed intramolecular C–N coupling are the key steps in the synthesis.