Alkene Coupling through Triflic Acid Elimination on Platinum(II)

The Pt(II) complexes (1,5-COD)Pt(OTf)2 and [(COD)Pt(THF)(OTf)]OTf react readily with alkenes (ethylene, cyclopentene, norbornenes) to give coupling products via HOTf elimination. With propylene a simple allyl complex is obtained

Reversible Alkene Extrusion from Platinaoxetanes

Reversible alkene extrusion from platinaoxetanes has been observed. Catalytic amounts of electrophilic Pt complexes, HOTf, Ag+, or BF3 (best) result in dramatic rate enhancements

Reversible Alkene Extrusion from Platinaoxetanes

Reversible alkene extrusion from platinaoxetanes has been observed. Catalytic amounts of electrophilic Pt complexes, HOTf, Ag+, or BF3 (best) result in dramatic rate enhancements

Alkene Oxidation by a Platinum Oxo Complex and Isolation of a Platinaoxetane

Oxo complex [(1,5-COD)4Pt4(μ3-O)2Cl2](BF4)2 (1) reacts readily with ethylene and norbornylene. The ethylene reaction yields acetaldehyde and a 1:1 mixture of (1,5-COD)Pt(Cl)(CH2CH3) (2) and [(1,5-COD)Pt4(η3-CH2CHCH(CH3))](BF4) (3), while the norbornylene reaction yields a platinaoxetane complex, the first metallaoxetane to be obtained from the reaction of an oxo complex and an alkene

Alkene Oxidation by a Platinum Oxo Complex and Isolation of a Platinaoxetane

Oxo complex [(1,5-COD)4Pt4(μ3-O)2Cl2](BF4)2 (1) reacts readily with ethylene and norbornylene. The ethylene reaction yields acetaldehyde and a 1:1 mixture of (1,5-COD)Pt(Cl)(CH2CH3) (2) and [(1,5-COD)Pt4(η3-CH2CHCH(CH3))](BF4) (3), while the norbornylene reaction yields a platinaoxetane complex, the first metallaoxetane to be obtained from the reaction of an oxo complex and an alkene

Aminotroponiminato Hafnium and Zirconium Complexes: Synthesis and Ethylene/1-Octene Copolymerization Study

Four new aminotroponiminato hafnium and zirconium tribenzyl complexes were prepared by reacting neutral ligands with the corresponding tetrabenzyl complexes. Aminotroponimine ligands were prepared in four steps starting from tropolone. An air-stable ethoxy-amino-tropylium cation intermediate isolated during ligand synthesis was found to react directly with amines significantly faster than the neutral intermediate proposed previously. This tropylium cation represents a convenient way to prepare a large array of aminotroponimines. An ethylene/1-octene copolymerization study conducted at 120 °C demonstrated that the aminotroponiminato hafnium and zirconium complexes are catalytically active, but their activity is lower than that observed for the corresponding imino–enamido complexes. Polymer analysis data (GPC and DSC) indicated that aminotroponiminato complexes generate at least two catalytically active species under polymerization conditions

Proton-Catalyzed Oxo−Alkene Coupling: 2-Platinaoxetane Formation

Proton-Catalyzed Oxo−Alkene Coupling: 2-Platinaoxetane Formatio

Proton-Catalyzed Oxo−Alkene Coupling: 2-Platinaoxetane Formation

Proton-Catalyzed Oxo−Alkene Coupling: 2-Platinaoxetane Formatio

Aminotroponiminato Hafnium and Zirconium Complexes: Synthesis and Ethylene/1-Octene Copolymerization Study

Four new aminotroponiminato hafnium and zirconium tribenzyl complexes were prepared by reacting neutral ligands with the corresponding tetrabenzyl complexes. Aminotroponimine ligands were prepared in four steps starting from tropolone. An air-stable ethoxy-amino-tropylium cation intermediate isolated during ligand synthesis was found to react directly with amines significantly faster than the neutral intermediate proposed previously. This tropylium cation represents a convenient way to prepare a large array of aminotroponimines. An ethylene/1-octene copolymerization study conducted at 120 °C demonstrated that the aminotroponiminato hafnium and zirconium complexes are catalytically active, but their activity is lower than that observed for the corresponding imino–enamido complexes. Polymer analysis data (GPC and DSC) indicated that aminotroponiminato complexes generate at least two catalytically active species under polymerization conditions

Polymerization of Norbornene and Methyl Acrylate by a Bimetallic Palladium(II) Allyl Complex

The sequential reaction of {(allyl)Pd(μ-Cl)}2 (2) with AgPF6 and PCy3 in CH2Cl2 generates a mixture (1-in situ) of [{(allyl)Pd(PCy3)}2(μ-Cl)][PF6] (1), 2, [(allyl)Pd(PCy3)2][PF6] (3), and (allyl)PdCl(PCy3) (4), which evolves to form pure 1 after 20 h at 23 °C. Complex 1 reacts with PCy3 to generate 3 and 4 and undergoes facile exchange of Pd units with 4. Both 1 and 1-in situ polymerize mixtures of norbornene (NB) and methyl acrylate (MA) to a mixture of poly(NB) and poly(MA) via competing NB insertion polymerization and MA radical polymerization