Molecular Catalysis of Rare-Earth Elements

241 Pages·2010·62.239 MB·English

by  Alexander L. Reznichenko, Kai C. Hultzsch (auth.), Peter W. Roesky (eds.)

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Molecular Catalysis
of Rare-Earth Elements
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With contributions by
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T. Li B. Liu A.L. Reznichenko P.W. Roesky
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ISSN0081-5993 e-ISSN1616-8550
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DedicatedtothememoryofProfessor
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organolanthanidechemistry
Preface
This volume reviews the recent developments in the use of molecular rare-earth
metal compounds in catalysis. Most of the applications deal with homogenous
catalysis but in some cases, heterogeneoussystems are also mentioned. The rare-
earthelements,whicharethelanthanidesandtheirclose relatives– scandiumand
yttrium – have not been in the focus of molecular chemistry for a long time and
therefore have also not been considered as homogenous catalysts. Although the
firstorganometalliccompoundsofthelanthanides,whicharetris(cyclopentadienyl)
lanthanide complexes, were already prepared in the 1950s, it was only in the late
1970s and early 1980s when a number of research groups began to focus on this
classofcompounds.Onereasonforthedevelopmentwastheavailabilityofsingle
crystal X-ray diffraction techniques, which made it possible to characterize these
compounds.Moreover,newlaboratorytechniquestohandlehighlyairandmoisture
sensitivecompoundsweredevelopedatthesametime.Concomitantwiththeacces-
sibilityofthisnewclassofcompounds,theapplicationinhomogenouscatalysiswas
investigated.Oneofthefirstapplicationsinthisfieldwastheuseoflanthanidemet-
allocenesforthecatalyticpolymerizationofethyleneintheearly1980s.Inthelast
twoorthreedecades,ahugenumberofinorganicandorganometalliccompoundsof
therare-earthelementsweresynthesizedandsome ofthemwerealso usedascat-
alysts.Althoughearlyworkinhomogenouscatalysisbasicallyfocusedonlyonthe
hydrogenationandpolymerizationofolefins,thescopeforcatalyticapplicationto-
dayismuchbroader.Thus,alargenumberofcatalyticσ-bondmetathesisreactions,
e.g.hydroamination,havebeenreportedintherecentyears.
Thisbookcontainsfourchaptersinwhichpartoftherecentdevelopmentofthe
use of molecular rare-earth metal compoundsin catalysis is covered.To keep the
book within the given page limit, not all aspects could be reviewed in detail. For
example, the use of molecular rare-earth metal complexes as Lewis acidic cata-
lystsisnotdiscussedinthisbook.Thefirsttwochaptersreviewdifferentcatalytic
conversions,namelythecatalyticσ-bondmetathesis(ChapterbyReznichenkoand
Hultzsch) and the polymerization of 1,3-conjugated dienes (Chapter by Zhang
et al.). Within these chapters, differentcatalytic systems and applications are dis-
cussed. The final two chapters are more concentrated on recent developments of