1395

J・CHEM・SOC・、CHEM・COMMUN・，I992
thesecondpolnt，thering−OPenlng−rlng−CloslngreaCtionof3

gave4，Which contains the aromaticl．2，4−OXadiazole（asformedheterocyclicring）．Accordingly，lwouldhavegiven5，
containlngthenon−arOmaticl，2・4−0Xadiazolerlng・througha

nucleophilic addition（AN）to the carbonylcarbon ofthethiazoloneintermediate7・Perhaps5is only an unstable

intemediate which collapses to80r alternatively7gives
directly8byanacylicnucleophilicsubstitution（SNAc）atthe

same atomwiththe cleavage ofthe feeblecarbonyl−Sulfur

bond・6Thethiolgroupof8inturnglVeS2byadditiontothe
ketoniccarbonylcarbon7andformationofasix一membered
CyClichemithioacetal・

The authors are gratefulto one ofthe referees for his
SuggeStionontheroleof5・

WethanktheCNRandMURSTforfinancialsupport・Soc．．PerkiI7

7TaIlS．2．1990．1289：（b）D．Spinelli、TheSis．

UniversltyOfBari．1955：S・CusmanoandM・Ruccia・Gaここ・CI〜tm・

IIal．．1955，85．1686：S．CusmanoandM．Ruccia、Gaここ．Chim．JIa／．．

1958．88．463．
3（a）A．Andreani．M．Rambaldi．F．Andreani、P．HreliaandG・
CanteIli・Forti．ArcIi．Pharm．CIleIn．，Sci．Ed．．1987．15工l：（b）P．
Hrelia．し．Murell主M．Paolini、E．SapigniandG．Cantelli−Forti、MilIageneSis工987、2，425andreferencescitedtherein・
4AnX−rayCryStalstruCturedeterminationconfirmedthestructureof

theobtainedproductas2（unpublishedwork）・

5E．Pretsch、T．Clerc．J．SeiblandW．Simon．7tlb／eSqrSpectralDaIa
jbr S個C他re DeterIninattO′i qf O′gatlic Co′，〜pO

nds・Springer−

Verlag、NewYork、2ndedn・∴989・
6InagreementwiththelowresonanceenergyOfthe−CO−S−grOuP・

thethioloestersshowamarkedtendencytOaCtaSaCylatIngagentS
ViaSNAcr竺Ctions・Thisreactivityiswellsupportedinchemical（OnthereactivltyOfthi01oesters、SeeM・J・Janssen・77zeCI〜e′7〜i5tryqf

Carbo。rYlicAcidsaIidESIerS．ed．S．Patai．Interscience．NewYork、Receiveti．30tIIMarch1992；CoIn．2／01670B

1969．pp．724andfollowing）andbiologicaI（Seetheroleofacetyl
COenZymeAinbiologicalacyIation）systems・
70ntllefastreactionofthioIswithketonestogi、ReferenCeS

Roque・Recl・T′・a一・・α〜iIn・Pa一，S・Bas・1972・91・1015‥M・E・Peach・

I DrtlgMeIaboIismiIlMa′！、ed．J．W．GorradandA．H．Beckett．
TaylorandFrancisLtd．London、1978．

2（a）M・Ruccia・N

ehemi亜oacetals

andthioacetals．see L．Fournier．A．Natat、G．LamatyandJ・P・
in777eC／〜e′nis〝yqflI〜e77ziblGrol

p、ed．S．Patai．Wiley．Ncw

York、1974．pp・765andf0110Wlng‥T・H・LowryandK・Schneller

VivonaandD・Spine帖Adt：HeI叩CJ）C／・C／一e′n・・

Richardson、AtecIiaIZiSInaI7（白rheoIyinOrga′JirCIle′nis時．Harper

1981．29．141：V・Frenna．D・SpinelliandG・Conslglio．J・CI〜e′n・andRow、3rdEd・・1987．pp・701−702andreferencescitedtherein・

SeiectiveSynthesisofOxYgenateSintheCO−H2ReactiononSupportedRuthenium
Carbido−clusterCatalysts
Y．lzum巨T．chihara．bH．YamazakibandY．Iwasawa篇aaDepartmentofChemistryJFacultyofScience，TheUniversityof7bkyo，Hongo，Bunkyo−ku，7bkyol13，Japanb777elnstituteofPhysicalandChemica／Research，Vthko−S朽Saitama351−01，Japan

Supportedrutheniumcarbido−Clustercatalysts〈lRu6C〈CO〉16Mel−／0Xide）selectiveIyproducedmethanoI．dimethYl

ether，andformaIdehYdeinCO−H2，incontrasttothepreferentialformationofmethaneandhYdrocarbonsonsupported
rutheniumclustercatalysts〈lRu6（CO〉1812−／0Xide〉Withouttheinterstitialcarbonandconventionalmeta帖cRucatalYStS・

Melalclustersareexpected10hal′eumqueCatalytlCPrOPerties

U−Shapedliquid−nitrogen trap for oxygenated compounds・

associatedWithmultiplemetalsites．whichareofgreatinterest

Beforethecatal、′ticreactionthefreshsampleswereactivatedfromchemicalandindustrialpolntSOfview・However．there

bvheatlngat623Kinvacuum．ThereactionproductSWere

are few examples of catalvsis specific to metal cluster

analysedbygaschromatographyusinga5AmolecularsieveframeWOrks that not obserVed witll the usual metal cat−

COlumn（2m）formethane．aVZ−10column（：m）forethenc、all′StS・1・2We report the catalvtic formation ofoxygenatedethaneandpropene．andaDOS（dioctylsebacate）column（4COmpOundsonsupportedrutheniumcarbido−Clusters・m）formethanol．dimethyletherandformaldehydc・Asshown［btmaI＋tRu6C（CO）16Me］￣l（btma＝COH5CH2NMeJ）3in Tablel the turnover frequencies fo‥he formation ofWaSSuPPOrtedoninorganicoxidesbvadsorptlOnat290Kfor

OXygenateS W

lhinpurifiedCH・Cl，andthesubsequentremovalofCH・Cl，lRu。1／OxidesortheconventlOnalimpregnatedcatalvsts・Those

undervacuum．TiOこ（DegussaP25：Surfacearea：60m2g￣1）．

TOFsforIRubCIIoxidesarFCOmPara里OrSuPeribrtothoseerelarger Pn tRu6Cl／0両es than those forZrO2（Soekawa．99．9％士2m：g￣l），A1203（DegussaAlonC；

forotherclustersystemsln the pre、・10uSliterature・6・7This

100m2g￣l），andSiO2（Fuji−Da、，ison．silicagelNo・952：300

SuPeriorityofthecarbido−Clusterwasindependento白llekindmlg￣l）weretreatedat473Kfor2hinvacuumbeforeuseas

Ofsupports．ThemostactiY′eIRu。Cl爪03PrOducedformal−

SuPPOrtS．ZnO（Kadox）wastreatedat773Kfor2h・MgO

dehyde（20％），methanol（12％）anddimethylether（9・6％）at（200mt g￣1）and La203（35m二g￣1）were prepared from

523K．andtheactivitvdidnotdecreaseover15h．Theorderof

Mg（OH）ユ（Soekawa．99．99％）and La（OH）3（Soekawa・

the activityofoxygenate synthesisforsupportwasTiOl＞

99．9％）bytreatmentat773Kfor2hinvacuum・Theloadings

A1203≧ZrO，＞La203＞SiO〕＝MgO＞ZnO・Supported

ofRuwerefixedto3．Owt％−RuforSi0，．2．Owt％forLaっ03，

1．8wt％forMgO．1．5wt％forTiO・andA1203，andl・Owt％

lRubClcluste玉alsoexhibitedhigherもecti、・itiestooxy・gen−atedcompoundsascomparedwithIRuol／oxidesandimpreg−

forZnOandZrO，．Thesupportedrutheniumcarbido−Clusters

nated．catalystsasshowninTablel・［Ru6CI／La‥03、㌧a：mOSt

aredenotedasiRubC］／oxide．

SelectlVe（92％at473K）．The order ofthe selectlVlty forlbtmal十二［Ru6（CO）1謹￣2↓・5WaSSuPPOrtedonLa203，TiO2
andAl203inacetoneinasimilarproceduretothecaseofl・

Thesupportedrulheniumclustersaredenotedas［Ru6lIoxide・

SuPpOrtWaSLa203＞MgO＝TiO2：＝ZrO2＞Alニ03＞SiO2≧

ZnO．
The dependency of the activity and selectivity of theConventionalRucatalvstsWerepreParedbvausualimpreg−lRu6ClIoxidecatalystsonthekindofsupportisfairlydifferent

nationmethodusinganaqueoussolutiondfRu（NO）（NO3）．

fromthatoftheusualimpregnatedRucatalyStS（Tablel）・Itis（N．E．Chemcat．Co．）．

to be noted that the ruthenium carbido−Cluster−derived

CO−H2reaCtionswerecarriedoutunderCOof14・6kPa

Catalystspreferentiallyproducedtheoxygenatedcompounds・

andH，Of14．6kPainthetemperaturerange473−523Kina

whiletheimpregnatedmetallicrutheniumcatalyStSprOduced

closed￣circulating system（dead volume‥133ml）with amainlymethaneandhydrocarbons・E、′enif、，ariousamounts

J．CHEM．SOC．，CHFM．COMMUN．．1992

1396

TablelTheturnoverfrequencies（TOF）andselectivitiesforthefomationofoxygenatesontheRucatalystsat473and523K

Precursor

Ru（NO）（NO高lRub（CO）1812￣

tRueC（CO）16Mel￣T，。。。．．IK

3．一1713一2．一0・1一〇・30・3一〇・5一〇一〇〇一4・2一〇 一 〇 〇 一 ⁝ 一一一233〇一十一742二〇・82・1一⁝一3873一一3727一2一4二〇・2⁝一〇・〇一l−1−0

110ノ 0 ︵lフ 4・0ノ7 ／〇0135・4 1 4 43207400 2 1tJ−tJ O

4tJ

4 2 ∩ブ一ヽ︶ 5 っJ 3

78 4 2 3 ●3．4 4105Sibユ

5La：Oj

TiO，Zrd二Al、OI0ZnO

0∩︺ O l nU 00

NIgO

010−3min−1．bmol％：CO（14．6kPa）．H2（14・6kPa）・

ofcarbideweredepositedonthemctallicRuparticles・thenm（N＝l・9）・RRu一〇二0・206nm（N＝l・8）・RRu‥C＝0・19lnmformationoftheoxygenatedcompoundswasnotobserved・Afterthe reductionof［Ru6C］IMgOwith H2at623Kthe（N＝0．9）．andRR。仁C＿）0＝0・299nm（N＝0 8）・Slmila申ftOthecase of the Ru3（CO）12−derived sample・6ThelRu誹Alニ03

catalvtic activities for the formation of the oxygenates

Catalystshowednegligibleorlowactivltyandselectivitvfor

decr；ased toO（473K）一35％（523K）ofthose before H2

thesynthesisofoxygenatesunderidenticalconditions・treatment，Tlle thermal desorptlOn eXPerimentsin Dl

Thus●thespecificformationoftheoxygenates・unliketherel′ealedtheformationofequlmOlarCDltOtheamountof

COhydrogenationofaC−Obond−breakingtypeontheusual［Ru。Clunitsonthe．望PPOrtSuPtO623K・Sugg専ngthc

impregnatedmetallicRucatalysts，maybeascribedto（i）theremovaloftheinterstltlalcarbonbyhydrogenreductlOnat623

elecfrOn−donating effect8￣一。of aninterstitialcarbon（orK．WhenasmallamountofmethanoltogetherwithCO＋H2

equlValent carbon），（ii）about six−ruthenlum Clusterframe−

wasintroducedinto thelRu6Cl／TiOヱCatalyst at523K・WOrk，and（iii）thenatureOfsupports・

methanoI was readilv convertedintO formaldehvde anddimethlrlether．InCO＋H，reaCtions，formaldehl・demavbe
produced viamethanol／methoxvlintermediatesratherthan

Receil・ed，19thMarch1992：CoIn．2／01468H
Recei↓・ediItreVisedfbrmlO高June1992

directlvfromCO＋H，．
We measured the Ru Kでdge EXAFS spectra for thecatalvststhcrmallv activatedatbeamline10Bofthe Photon

FactorvintheNationalLaboratorvforHighEnergvPhvsics（proposalNo・91012）・Thecurve血tinganalysisshowedthe

Ru−RubonddistancesofO．2611）．263nmforlRu。Cl／MgO・lRu。Cl／La：03．lRu。Cl／TiOユandIRubC］／A120〕・Thesevalues
areclosetothatforRumetal．Thecoordinationnumbers（N）

for the Ru−Ru bond were3．3−4．4Similar to that for theoriginalclusterl．Wllenthe［RuhCI／MgOcatalystW●aStreatedReferences
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dam・1986・

71IiIoI■ett Melal Cata／liS高、ed．Y．Iwasawa．Reidel．Dordrecht、1986．
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1990．383．367．

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4C・HavWardandJ・R・Sharpley・／′〜Org・CI〜e′rL1982・21・3816・

reproduced・Sl10Wlngthesamebonddistancesandcoordina−

5C．R．Eadv．P．F．Jackson．B．F．G．Johnson．J．Lewis、hl．C．

tion numbers for Ru−Ru and Ru（−C−）Ru as those forlas

Malatesta．M．McPartlin and W．J．H．Nelson、）．CIIeIn．50C．．

provedbvEXAFS・ThisreversibilitvoftheciusterStruCture

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a RuO unit and a carbide atom bv activation at623Kin

DflltOIl n■an5．．1980．383．

6K．Asakura．K．Bandoand Y．Iwasawa．！．C／leIIL Soで．．Ftzradal，

れa部．．1990．86．2615．
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Ll・・1990・126・13工

8J．F．Halet．D．G．El・anSandM．P．MingOS、J〟，AIn．CIieIn．Soc，、IncontrasltOthesesamplestRu。Cl／SiO〕（NRu−R。＝6・6）
aggrcgatedb、・thepretreatmentat623K・Thiscatalvstwas

mu．hlessaiti、′ethantheIRu。CI／TiO2Catalyst（T誼el）・［Ru。1／Al⊇03WithoutillterStitialcarbonwasdegradatedtoan
oxy・gen−incol
POratedclusterwhichexhibitSRRu・Ru＝0・261

1988．110．87．
9R．MasonandW．R．Robinson．！．ClleIn．Soc．，CIIeIn．CoInI7硝I！．．

1968．168．
10G．B．AnsellandJ．S．Bradlev、AcIaCI・1所a／Iogr．．Sect．B．1980、36．726．

lntercalationofPolyethersintotheMPS3（M＝Mn，Cd）HostLatticelsabeileLagadic．AnneLeausticandReneClement持しaboratoiredeChimieInorganique，CNRSURA420，UniversiteParisSud，914050rsayCedex，France

Po−yethyleneoxideandpoIYethYleneglYCOIscanbeinsertedintoMPS31ayeredmateriaIspre而ercaiatedwithhydrated

meta帖ccations．

Insertion of polymersintoinorganiclow−dimensional

exchangeafractionoftheMZ＋intralayercations・6・7Air−StablematerialsisatopICOfrecentinterestandonlvafewexamples

interealatescanthusbeobtained，Whichinsome caseshave

havebeendcscribedsofar十5Amongthelaveredtransition

physicalpropertiesverydifferentfromthoseofthepurehost

metalchalcogenidcs．the MPS3materials possess a unlquelattices・8・gInordertoobtainneworgano一mineralcomposite

intercalation chemistrv based on the abilitv ofthelattice tohostlattices and possible●supported、solidelectroIvtes，We