Synthesis and Characterization of Rh—Co Butterfly Clusters Capped by Functionally Substituted 1—Alkynes

1INTRODUCTIONThemixed-transition-metalclustershavehighpotentialtoserveasefficientcatalystsforavarietyofhomogeneouscatalyticreactionsaswellasuniquereagentsfororganicsyntheses[1].Ithasbeenreportedthatthereactionsof[Rh2Co2(CO)12]withseveralalkynestogiveRh-Comixed-metalbutterflyclusters[1～4].Inaddition,thereactionofsilylformylationof1-hexynewiththehydro-formylationofcyclohexene,1-penteneandstyrenehavealsobeeninvestigatedbyusing[Rh2Co2(CO)ascatalyst[5].Inordertogainmoreunderstandingaboutt…     

Synthesis and Crystal Structure of O,O'-Diisopropyl-5-(4-chlorophenyl)-1-hydroxy-2E,4E-pentadienylphosphonate

1　INTRODUCTIONAbscisicacid(ABA)isoneofplanthormoneswhichwasisolatedfromyoungcottonfruitsin1963[1].Itnotonlyinhibitsplantgrowth,butalsoprotectsplantsa-gainstdeprivationofwaterduringdroughtdays[2].Hydroxyalkylphosphonicacidsandtheirderivativesappeartobeveryimportantfortheirwidebiologicalactivitiesintheinhibitionofenzymes,fungicidesandplantgrowthregulation[3].Wedesignedandsynthesizedthetitlecompound4,theunsaturatedphosphonateanaloguesofABA,whichexhibitsplantinhibitoryactivityontheelongati…     

PREPARATION OF POLY (LACTIC ACID)THROUGH THIONYL CHLORIDE ACTIVATED POLYCONDENSATION

1.INTRODUCTIONBiodegradablelacticacidpolymershavebeenwidelyusedinthebiomedicalfield[1-4].Ithasbeencurrentlyrecognizedasasuitablematerialforpackagingandconsumergoodsduetoitsseveralpreferableproperties,suchasmechanicalstrength,transparency,safetyanddegradabilityincompost[5].Poly(lacticacid)canbeproducedbycondensationpolymerizationoflacticacidorbyringopeningpolymerizationoflactide,whichisthedilactoneoflacticacid.Highmolecularweightpoly(lacticacid)wassynthesizedbyringopeningpolymerizationofla…     

Synthesis and Crystal Structure of 1-[(1′-Phenyl-5′-methyl-4′-pyrazolcarbonyl)- 3-methylthio-5-amino-1H-yl-1,2,4-triazole

1INTRODUCTIONTheCIDT(N-cyanoimido-S,S-dimethylthiocarbo-nate)hasbeenwidelyutilizedinorganicsynthesisduringthelasttwodecadesandhasbecomeveryusefulforconstructingfunctionalizedheterocyliccom-poundsbecauseoftheirversatility.MuchattentionhasrecentlybeenfocusedonthedevelopmentofCIDTaswellastheirsyntheticapplications[1～4].Meanwhile,manypyrazoleandtriazolederivativesarereportedtoshowvariousbiologicalactivities,suchasantifungal[5],herbicidal[6～8],insectcidal[9]andotheractivities[10～12].Thu…     

Two Side Chain β-CD Polysiloxanes Used as New Stationary Phase for Chiral Separation by HRGC

SinceJuvancefirstapp1iedpermethylated6-CDascapillarygaschromatographic(CGC)stationarephase[l],alot0fCDderivativeshavebeenwideIyusedaschiralstationaryphase(CSP)fortheseparation0fchiralvolati1es[2].Furthermore,inordertogainCDcolumnwithhigherthermalstabi1ityandl0``Terb1eed,afewstationaryphases,thatCDderivativesb0ndedt0apo]ysiloxanebackbone-weresynthesizedbyFischer[3]andbySchurig[4].Thesestationaryphasesexhibitnoton]}'goodthermalstabilitybutalsoextensiveenantiomerse1ectivityinGCandSFCsepa…     

Abnormal IR Spectra of CO Adsorbed on the Surface of Glass Carbon Electrode Modified with Polypyrrole Film with Platinum Microparticles

Recentiy,inCorPOhoonOfPtorPdInic~clesintocondUedngpolyInfilmsmededonthee1eCtrodechwasstudied.ThemalledelnddsedexCellenteleCtr~cactivitiesintheOkidationOfsInallOrgbocmolecules[l-3].ItwasreportedthattheglaSs~GC)electrthemalledwithapotwrrOleop)filmwithPtndcrOPanides(Pt/PWGCelectrode)shedaconsiderabfyhighereleCtrOCatalyticactivitythanthaOfthebarPtelectrodefortheOaldationOfmethanol[3].ItiswellknownthadurngtheOkidationOfmethanol,COcanbeProdUedandposonthePtanode,leading'tothedeceasei…     

ADSORPTION OF SAMARIUM(III) ON DIGLYCOLAMIDIC ACID RESIN

1.INTRODUCTIONThesynthesis,characterizationandsorptionpropertyofpolymericmaterialshavebeenstudiedbytheauthorsandotherresearchersinrecentyears[1~9].Diglycolamidicacidresin(DAAR)isanovelpolymericmaterialwhichcontainsafunctionalgroup[-N(CH2COOH)2].Itnotonlypossessesprotonthatcanexchangewithcation,butalsooxygenatomsthatcancoordinatedirectlywithmetalions.SoDAARcanbewidelyusedinthesorptionofmetalions.Inthisarticle,thesorptionpropertiesofDAARforSm(III)wereinvestigated.Somebasicsorption…     

Synthesis, Crystal Structure and Spectrometry Study of Chiral N-Ethyl-N''''-(2'''',3'''',4'''',6''''-tetra-O-acetyl-β-D-glycosyl)-thiocarbamide

1INTRODUCTIONManynomadicsugarsperformimportantbio-logicalfunctions[1].Theycancontrolvariousgeneexpressionstoadjusttheupgrowth,developmentandreactionoforgans[2].Glycosylisothiocyanateshavebeenwidelyusedasvaluableintermediatesinthesynthesisofglycosylderivatives[3].Theiso-thiocyanatesandglycosylisothiocyanateshavebeenthefocusofsyntheticattentionduringrecentyearsbecauseoftheirpotentialpharmacologicalproperties[4].Theyhavealsoattractedconsiderableinterestduetotheanti-HIVactivityshownby1-deoxy…     

稀土铽离子对辣根过氧化物酶活力指数的影响(英)

0IntroductionHorseradishperoxidase(HRP)isaplanthemeenzymecatalyzingoxidationofawidevarietyofaro鄄maticmoleculesbyhydrogenperoxideanditisthemostwidelystudiedmemberoftheperoxidasefamily[1~3].ThecrystalstructureofHRPhasbeensolved[2].ThestructuralfeaturesofHR…     

Synthesis and Crystal Structure of 3,4—Bis（azidoacetamino）furazan

1INTRODUCTIONDuringthepastthreedecades,1,2,5-oxadiazole(furazan)hasbeenstudiedintheN.D.ZelinskyInstituteofOrganicChemistry[1,2],anditwasfoundthatthearomaticityoffurazanringusuallyincreasesthethermalstabilityofitsderivativesandtheplanarityoftheringprovidesthemwithhighdensity.TheweaknessoftheNObondsinfurazanwassuggestedbyananalysisofitsmass-spectrum[3].Itagreeswiththeresultsoftheresonanceformsoffurazan,whichiscalculatedbySaegebrath[4].Thereby,whenthechloroacetaminogroupwasintroducedintot…     

键长和电子效应共同调控的β-二酮Dy(Ⅲ)配合物的合成、结构与磁性

以N-乙基-3-吲哚三氟甲基β-二酮(EIFD)为主配体,分别以乙二醇单甲醚(EM)、乙二醇二甲醚(EDM)、二缩三乙二醇(TEG)为辅助配体,与DyCl3·6H2O反应合成了一系列Dy(Ⅲ)配合物[Dy(EIFD)3(EM)]·CH2Cl2(1)、[Dy(EIFD)3(EDM)]·CH2Cl2(2)和[Dy(EIFD)3(TEG)](3)。X射线单晶衍射分析表明,3个配合物都是八配位的单核结构,配位构型分别为双帽三棱柱、正十二面体和双帽三棱柱,分别具有C2v、D2d和C2v对称性。磁学性质显示了配合物1~3具有慢弛豫现象,能垒分别为95.1 K (1)、40.5 K (2)、53.8和13.4 K (3),且配合物1和3有明显的蝴蝶状磁滞回线。进一步讨论了配合物中Dy-O键长和含氧辅助配体的电子效应对配合物有效翻转能垒的影响。     

Formation and chemical reactivities of a new type of double-butterfly [[Fe2(mu-CO)(CO)6]2(mu-SZS-mu)]2-: synthetic and structural studies on novel linear and macrocyclic butterfly Fe/E (E=S,Se) cluster complexes

A new type of double-butterfly [[Fe(2)(mu-CO)(CO)(6)](2)(mu-SZS-mu)](2-) (3), a dianion that has two mu-CO ligands, has been synthesized from dithiol HSZSH (Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)), [Fe(3)(CO)(12)], and Et(3)N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E=S, Se) cluster complexes. For instance, while reactions of 3 with PhC(O)Cl and Ph(2)PCl give linear clusters [[Fe(2)(mu-PhCO)(CO)(6)](2)(mu-SZS-mu)] (4 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)) and [[Fe(2)(mu-Ph(2)P)(CO)(6)](2)(mu-SZS-mu)] (5 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2)), reactions with CS(2) followed by treatment with monohalides RX or dihalides X-Y-X give both linear clusters [[Fe(2)(mu-RCS(2))(CO)(6)](2)(mu-SZS-mu)] (6 a-e: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2), FeCp(CO)(2)) and macrocyclic clusters [[Fe(2)(CO)(6)](2)(mu-SZS-mu)(mu-CS(2)YCS(2)-mu)] (7 a-e: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2); Y=(CH(2))(2-4), 1,3,5-Me(CH(2))(2)C(6)H(3), 1,4-(CH(2))(2)C(6)H(4)). In addition, reactions of dianions 3 with [Fe(2)(mu-S(2))(CO)(6)] followed by treatment with RX or X-Y-X give linear clusters [[[Fe(2)(CO)(6)](2)(mu-RS)(mu(4)-S)](2)(mu-SZS-mu)] (8 a-c: Z=CH(2)(CH(2)OCH(2))(1,2)CH(2); R=Me, PhCH(2)) and macrocyclic clusters [[[Fe(2)(CO)(6)](2)(mu(4)-S)](2)(mu-SYS-mu)(mu-SZS-mu)] (9 a,b: Z=CH(2)(CH(2)OCH(2))(2,3)CH(2); Y=(CH(2))(4)), and reactions with SeCl(2) afford macrocycles [[Fe(2)(CO)(6)](2)(mu(4)-Se)(mu-SZS-mu)] (10 d: Z=CH(2)(CH(2)OCH(2))(3)CH(2)) and [[[Fe(2)(CO)(6)](2)(mu(4)-Se)](2)(mu-SZS-mu)(2)] (11 a-d: Z=(CH(2))(4), CH(2)(CH(2)OCH(2))(1-3)CH(2)). Production pathways have been suggested; these involve initial nucleophilic attacks by the Fe-centered dianions 3 at the corresponding electrophiles. All the products are new and have been characterized by combustion analysis and spectroscopy, and by X-ray diffraction techniques for 6 c, 7 d, 9 b, 10 d, and 11 c in particular. X-ray diffraction analyses revealed that the double-butterfly cluster core Fe(4)S(2)Se in 10 d is severely distorted in comparison to that in 11 c. In view of the Z chains in 10 a-c being shorter than the chain in 10 d, the double cluster core Fe(4)S(2)Se in 10 a-c would be expected to be even more severely distorted, a possible reason for why 10 a-c could not be formed.     

C-H cleavage and double alkyl additions to the disulfido ligand in dicyanido-bridged Ru2S2 complexes

Novel dicyanido-bridged dicationic RuIIISSRuIII complexes [{Ru(P(OCH3)3)2}2(mu-S2)(mu-X)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (4, X=Cl, Br) were synthesized by the abstraction of the two terminal halide ions of [{RuX(P(OCH3)3)2}2(mu-S2)(mu-X)2] (1, X=Cl, Br) followed by treatment with m-xylylenedicyanide. 4 reacted with 2,3-dimethylbutadiene to give the C4S2 ring-bridged complex [{Ru(P(OCH3)3)2}2{mu-SCH2C(CH3)=C(CH3)CH2S}(mu-X)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (6, X=Cl, Br). In addition, 4 reacted with 1-alkenes in CH3OH to give alkenyl disulfide complexes [{Ru(P(OCH3)3)2}2{mu-SS(CH2C=CHR)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3) (7: R=CH2CH3, 9: R=CH2CH2CH3) and alkenyl methyl disulfide complexes [{Ru(P(OCH3)3)2}2{mu-S(CH3)S(CH2C=HR)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (8: R=CH2CH3, 10: R=CH2CH2CH3) via the activation of an allylic C-H bond followed by the elimination of H+ or condensation with CH3OH. Additionally, the reaction of 4 with 3-penten-1-ol gave [{Ru(P(OCH3)3)2}2{mu-SS(CH2C=CHCH2OH)}(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3) (11) via the elimination of H+ and [{Ru(P(OCH3)3)2}2(mu-SCH2CH=CHCH2S)(mu-Cl)2{mu-m-C6H4(CH2CN)2}](CF3SO3)2 (12) via the intramolecular elimination of a H2O molecule. 12 was exclusively obtained from the reaction of 4 with 4-bromo-1-butene.     

Dehydration reaction of hydroxyl substituted alkenes and alkynes on the Ru(2)S(2) complex

A variety of inter- and intramolecular dehydration was found in the reactions of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C(3)S(2) five-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CH(OCH(2)CH=CH(2))S]](CF(3)SO(3))(4) (2), via C-S bond formation after C-H bond activation and intermolecular dehydration. On the other hand, intramolecular dehydration was observed in the reaction of 1 with 3-buten-1-ol giving a C(4)S(2) six-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2) [mu-SCH(2)CH=CHCH(2)S]](CF(3)SO(3))(4) (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCR=CHCH(OCH(2)C triple bond CR)S]](CF(3)SO(3))(4) (4: R = H, 5: R = CH(3)), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OH)S]](CF(3)SO(3))(4) (6), was isolated, which further reacted with 2-propyn-1-ol and 2-butyn-1-ol to give 4 and a cross-coupling product, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OCH(2)C triple bond CCH(3))S]](CF(3)SO(3))(4) (7), respectively. The reaction of 1 with diols, (HO)CHRC triple bond CCHR(OH), gave furyl complexes, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SSC=CROCR=CH]](CF(3)SO(3))(3) (8: R = H, 9: R = CH(3)) via intramolecular elimination of a H(2)O molecule and a H(+). Even though (HO)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OH) does not have any propargylic C-H bond, it also reacts with 1 to give [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)C(=CH(2))C(=C=C(CH(3))(2))]S](CF(3)SO(3))(4) (10). In addition, the reaction of 1 with (CH(3)O)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OCH(3)) gives [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(2)][mu-S=C(C(CH(3))(2)OCH(3))C=CC(CH(3))CH(2)S][Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)]](CF(3)SO(3))(4) (11), in which one molecule of CH(3)OH is eliminated, and the S-S bond is cleaved.     

1R,3S-1,2,2-三甲基-1,3-环戊二胺为配体的铂髤配合物的合成、表征和抗肿瘤活性

本文合成了9种含有由天然D( )鄄樟脑衍生的1R,3S鄄1,2,2鄄三甲基鄄1,3鄄环戊二胺(A)为配体的铂髤配合物[Pt髤AX]{其中,X=(CH2)3C(COO-)2(1,1鄄环丁烷二羧酸根),2CH3OCH2COO-,2CH3CH2OCH2COO-,2CH3(CH2)3OCH2COO-,[OCH(CH3)COO]2-(乳酸根),(OCH2COO)2-(乙醇酸根),2CH3OCH2CH2OCH2COO-,2CH3CH2OCH2CH2OCH2COO-和2CH3(CH2)3OCH2CH2OCH2COO-}。通过元素分析、热重分析、红外光谱、1H核磁共振谱和电喷雾质谱等对配合物进行了表征。体外生物活性测试表明,部分配合物对A549人肺癌细胞和HCT鄄116人结肠癌细胞具有较强的抗肿瘤活性。     

Syntheses, derivatives, solubility, and interfacial properties of 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: potential building blocks for syntheses of amphiphatic macromolecules

2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me(3)Si)(2)NH and toluenesulfonyl chloride (TsCl) to give mainly CH(3)C(CH(2)OSiMe(3))(3) (1), and CH(3)C(CH(2)OTs)(3) (2), respectively. With allyl bromide, the products were CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(2)(CH(2)OH) (3) and CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(CH(2)OH)(2) x H(2)O (4). The reactions of 4 with perfluoroalkyl iodides (R(f)I) were catalyzed by Cu(I)Cl to form 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: (R(f)CH=CHCH(2)OCH(2))C(Me)(CH(2)OH)(2) [R(f) = C(4)F(9) (5), C(8)F(17) (6), and (CF(2)CF(2))(4)OCF(CF(3))(2) (7)]. Reduction of 5 and 6 with hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium salt of 9 was reacted with allyl bromide or acetyl chloride to form (C(8)F(17)CH(2)CH(2)CH(2)OCH(2))C(Me)(CH(2)OX)(CH(2)OH)(2) [where X = CH(2)CH=CH(2) (10) or C(O)CH(3) (12)] and (C(8)F(17)CH(2)CH(2)CH(2)OCH(2))C(Me)(CH(2)OX)(2) [where X = CH(2)CH[double bond]CH(2) (11) or C(O)CH(3) (13)]. Reaction of tolenesulfonyl chloride with 7 gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium salt of 4 gave (4-CF(3)C(6)H(4)CH(2)OCH(2))C(Me)(CH(2)CH[double bond]CH(2))(CH(2)OH) x H(2)O (15). The compounds were characterized by NMR ((1)H, (13)C, (19)F, (29)Si), GC-MS, and high-resolution MS or elemental analyses. UV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si(CH[double bond]CH(2))(4) in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It crystallized in the monoclinic space group P2(1)/c, and unit cell dimensions were a = 24.966(2) A (alpha = 90), b = 6.1371(6) A (beta = 100.730(2)), and c = 10.5669(10) A (gamma = 90).     

Synthesis and structure of new carborane-substituted cyclotriphosphazenes

The reactions of [N(3)P(3)Cl(6)] with one, two, or three equivalents of the difunctional 1,2-closo-carborane C(2)B(10)H(10)[CH(2)OH](2) and K(2)CO(3) in acetone have been investigated. These reactions led to the new spiro-closo-carboranylphosphazenes gem-[N(3)P(3)Cl(6-2n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (1), 2 (2)) and the first fully carborane-substituted phosphazene gem-[N(3)P(3)[(OCH(2))(2)C(2)B(10)H(10)](3)] (3). A bridged product, non-gem-[N(3)P(3)Cl(4)[(OCH(2))(2)C(2)B(10)H(10)]] (4), was also detected. The reaction of the well-known spiro derivatives [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)] and [N(3)P(3)Cl(4)(O(2)C(12)H(8))] with the same carborane-diol and K(2)CO(3) in acetone gave the new compounds gem-[N(3)P(3)(O(2)C(12)H(8))(3-n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (5) or 2 (6), respectively), without signs of intra- or intermolecularly bridged species. Upon treatment with NEt(3) in acetone, compound 5 was converted into the corresponding nido-carboranylphosphazene. However, the reaction of gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5) with NEt(3) in ethanol instead of acetone proceeded in a different manner to give the new compound (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7). For compounds with two 2,2'-dioxybiphenyl units, gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5), (NHEt(3))[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(9)H(10)]] (8), and (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7), a mixture of different stereoisomers may be expected. However, for 5 and 7 only the meso compounds seem to be formed, with the same (R,S)-configuration as in the precursor [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)]. The reaction of 5 to give 8 seems to proceed with a change of configuration at one phosphorus center, giving a racemic mixture. The crystal structures of the nido-carboranylphosphazenes 7 and 8 have been confirmed by X-ray diffraction methods.     

Synthesis of open and closed metallacages using novel tripodal ligands: unusually stable silver(I) inclusion compound

The tripodal ligand 1,3,5-(CH3)3C6[CH2OCH2C(pz)3]3 (L1, pz=pyrazolyl ring) reacts with AgBF4 to yield ([L12Ag3(CH3CN)](BF4)3).(CH3CN)4, an inclusion complex in which the encapsulated acetonitrile cannot escape the triangular cage unit in either the solid or solution phase. The analogous hexatopic ligand C6[CH2OCH2C(pz)3]6 forms a 2-dimensional polymer composed of similar triangular cage units, again with the encapsulation of one acetonitrile molecule, linked by the additional tris(pyrazolyl)methane units. In contrast, the complex formed with L1 and Cd2+ has a double, open cage structure holding two diethyl ether molecules.     

Synthesis and Crystal Structure of {(PPh3)2ClRu(μ-Cl)-Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O)

The title compound has been synthesized by the reaction of [RuCl2(PPh3)3] and closo-[B10H10]2- in (CH3)2CHOH solution. Crystals suitable for a single crystal X-ray diffraction analysis were obtained from n-pentane diffused to CH2Cl2 solution. The crystal {(PPh3)2ClRu(μ-Cl)Ru(PPh3)B10H7[OCH(CH3)2]3}·0.4(H2O) is monoclinic , space group P21/n , Mr=1359.47, with a=19.434(4), b =14.340(4), c=25.865(9)(A), β= 95.48(3)°, V=7175(4)(A)3, Dc=1.258 g/cm3, Z=4, λ(MoKα)=0.71073(A),μ=6.03 cm-1, F(000)=2784, R=0.0631, wR2= 0.1425, S=1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh3)RuB10H7[OCH(CH3)2]3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.     

混合三烃基锡有机酸酯化合物构效关系 （Ⅰ）二环己基－甲基－2，4－二溴－β－甲基苯氧乙酸锡酯 及二环己基－甲基－2－甲氧基－4－丙烯基苯氧乙酸锡酯的晶体结构和分子结构

报道２，４－Ｂｒ２Ｃ６Ｈ３ＯＣＨ（ＣＮ３）ＣＯ２Ｓｎ（Ｃ６Ｈ１１）２ＣＵ３（１）和２－ＯＣＨ３－４－ＣＨ３ＣＨ＝ＣＨＣ６Ｈ３ＯＣＨ２ＣＯ２Ｓｎ（Ｃ６Ｈ１１）２ＣＨ３（Ｈ２Ｏ）（Ⅱ）的晶体结构和分子结构。（Ⅰ）单斜晶系，空间群Ｐ２１／ｃ，ａ＝１３．０６７（３），ｂ＝１０．５９４（３），ｃ＝１８．１５７（４），β＝１０６．９９（２）°，Ｚ＝４，Ｄｃ＝１．６７２ｇ／ｃｍ３，Ｖ＝２４０３．７３，μ＝４３．７３１ｃｍ－１，Ｍｒ＝６２２．９９，Ｆ（０００）＝１２３２；（Ⅱ）单斜晶系，空间群Ｐ２１／ｎ，ａ＝１０．４０９（１），ｂ＝　１２．５７０（２），ｃ＝２０．６６４（２），β＝８３．５１（１）°，Ｚ＝４，Ｄｃ＝１．２８１ｇ／ｃｍ３，Ｖ＝２６８６．４Ａ３，μ＝９．７６１ｃｍ－１，Ｍｒ＝５３９．２８，Ｆ（０００）＝１１２０．最后的偏离因子，化合物（Ⅰ）Ｒ＝０．０４６，Ｒω＝０．０４６；化合物（Ⅱ）Ｒ＝０．０４９，Ｒω＝０．０４７。晶体结构解析表明，化合物（Ⅰ）和（Ⅱ）中的锡均被配体的３个碳和２个氧原子配位，配位原子呈畸变三角双锥构型；化合物中的环己基均为椅式构象；化合物（Ⅱ）中，配位水分子和另一分子的羰基氧与芳环上的甲基氧?