0000000000132357

AUTHOR

Stéphane Bredeau

showing 4 related works from this author

Zirconocene [Cp2Zr] synthon and benzynezirconocene complexes as tools in main group element chemistry

1998

Abstract Interactions between zirconocene or benzyne zirconocene and unsaturated species incorporating main group elements lead to a variety of new metallaheterocycles. Efficient new methodologies of regiospecific syntheses of mono-, bi-, or tricyclic systems incorporating phosphorus, nitrogen, selenium, antimony, germanium or tin are reported.

Inorganic ChemistrychemistryAntimonyMain group elementSynthonMaterials Chemistrychemistry.chemical_elementOrganic chemistryGermaniumPhysical and Theoretical ChemistryTinAryneSeleniumCoordination Chemistry Reviews
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Versatile behavior of conjugated diynes with zirconocene reactive species

2008

Thermal decomposition of Cp2ZrPh2 in the presence of the buta-1,3-diynes RC≡CC≡CR (R = Ph, SiMe3) can lead to seven- or five-membered metallacycles. In both cases a stable benzo-fused seven-membered zirconacyclocumulene arising from a 2-fold insertion of the triple bonds of the dialkyne in the in situ generated zirconocene benzyne is formed. In the case of Me3SiC≡CC≡CSiMe3 a second minor complex is isolated: a 3-alkynyl-substituted zirconaindene arising from a β monoinsertion of one acetylenic function of the conjugated diyne in the zirconocene benzyne. No stable 2-alkynyl-substituted zirconacycle was isolated. This α monoinsertion complex is an intermediate in the exchange of the metalated…

010405 organic chemistryChemistrycycloaddition reactionOrganic ChemistryThermal decomposition[ CHIM.COOR ] Chemical Sciences/Coordination chemistrychemistry.chemical_elementmetalationConjugated system010402 general chemistryTriple bond01 natural sciencesAryne0104 chemical sciencesInorganic ChemistrycyclometalationAntimonyReagentAtomPolymer chemistryMoiety[CHIM.COOR]Chemical Sciences/Coordination chemistryzirconocene- benzyn intermediatePhysical and Theoretical ChemistryComputingMilieux_MISCELLANEOUS
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Coupling of Benzynezirconocene with 1,4-Diphenyl-1,3-butadiyne

2000

The thermolysis of diphenylzirconocene in the presence of 1,4-diphenyl-1,3-butadiyne to yield the seven-membered zirconacyclocumulene 1 via the intermediacy of benzynezirconocene is described. This complex has been characterized by an X-ray diffraction study. Additionally, better knowledge of the bonding of the cumulene moiety was achieved by DFT calculations. Cleavage of the Zr−C bonds of 1 with methanol provided the corresponding butatriene 2.

DiffractionOrganic ChemistryThermal decompositionCumulenePhotochemistryCleavage (embryo)Inorganic ChemistryCoupling (electronics)chemistry.chemical_compoundchemistryYield (chemistry)MoietyMethanolPhysical and Theoretical ChemistryOrganometallics
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Reactions of titanocene-bis(trimethylsilyl)ethyne complexes with diethynylsilane derivatives

2001

Titanocene complexes [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 4 and 5) react uniformly with siladiynes R 2 2 Si(CCR 1 ) 2 , where R 1 =Ph, and R 2 =Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η 5 -cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η 5 -C 5 H 5− n Me n ) 2 Ti{R 1 2 C 4 (SiR 2 2 )}]. Products arising from [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 2 (1,3-isomer), 4 and 5) and Me 2 Si(CCCMe 3 ) 2 vary with n : the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated t…

SilanesTrimethylsilylOrganic ChemistryBiochemistryOxidative additionInorganic Chemistrychemistry.chemical_compoundCrystallographyCyclopentadienyl complexchemistryHydrocarbon solventsX-ray crystallographyMaterials ChemistryPhysical and Theoretical ChemistryJournal of Organometallic Chemistry
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