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RESEARCH PRODUCT
Syntheses and reactivity of oxo niobocene complexes Cp*2Nb(O)X (X=H, OCH3) and crystal structures of [Cp*2Nb(OH)F]BF4 and Cp*2Nb(O)OC(O)H (Cp*=η5-C5Me5)
Jean-claude LeblancAndré SadorgeWalter MeierHenri BrunnerBernd NuberSandrine RignyDominique LucasYves MugnierClaude MoïseJoachim Wachtersubject
StereochemistryOrganic ChemistryProtonationCrystal structureElectrochemistryBiochemistryMedicinal chemistryIonInorganic Chemistrychemistry.chemical_compoundchemistryMaterials ChemistryReactivity (chemistry)FormatePhysical and Theoretical ChemistryFluorideStoichiometrydescription
Abstract Reaction of Cp*2NbCl2 (Cp*=η5-C5Me5) with KOH or Ba(OH)2·8H2O in THF forms the complexes Cp*2Nb(O)X (X=Cl: 2, H: 3). The ratio of 2 and 3 depends on the stoichiometry. If NaOMe is added or MeOH in solution Cp*2Nb(O)OMe 4 is formed in good yields. Reactivity studies with 3 and 4 show that the NbO as well as the Nb–X unit behave as chemically active sites. Protonation of 3 or 4 with HBF4 is followed by an attack of fluoride (from BF4− anion) to give [Cp*2Nb(OH)F]BF4 6 and [Cp*2NbF2]BF4 7. In contrast the reaction of 3 or 4 with HCO2H results in an exchange of X− by formate to give Cp*2Nb(O)OC(O)H 8. The crystal structures of 6 and 8 are reported. Electrochemical investigations of 2–4 and 7, 8 reveal reaction pathways for the transformation of 1 into 3.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1998-09-01 | Journal of Organometallic Chemistry |