Thermal reaction of a (hydrido)(selenolato)platinum(II) complex having a dibenzobarrelenyl group leading to three cyclometalations.
The thermal reaction of a (dibenzobarreleneselenolato)(hydrido)platinum(ii) complex gave two four-membered selenaplatinacycles, one of which is formed by hydroplatination of the Pt-H bond to the etheno bridge and the other is a vinylic C-H bond activation product, and a five-membered selenaplatinacycle formed by an aromatic C-H bond activation.
Regioselective Attack of a Soft Carbon Nucleophile and Hydrogen Sulfide at the Central Carbon of a β-Substituted η3-Allyl To Respectively Form η3-TMM and New Metallacyclic Thiacyclobutane Complexes†
The cationic β-substituted allyl complexes {Pt(PPh3)2[η3-CH2C(OE)CH2]}+ (E = silyl, alkyl, acyl) undergo the substitution of the carbon nucleophile for OE at the allyl central carbon to transform into η3-TMM complexes or undergo addition by hydrogen sulfide to yield new metallathiacyclobutane complexes.
Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis
With petroleum supplies dwindling, there is increasing interest in selective methods for transforming other carbon feedstocks into hydrocarbons suitable for transportation fuel. We report the development of highly productive, well-defined, tandem catalytic systems for the metathesis of n-alkanes. Each system comprises one molecular catalyst (a “pincer”-ligated iridium complex) that effects alkane dehydrogenation and olefin hydrogenation, plus a second catalyst (molecular or solid-phase) for olefin metathesis. The systems all show complete selectivity for linear (n-alkane) product. We report one example that achieves selectivity with respect to the distribution of product molecular weights, in which n-decane is the predominant high-molecular-weight product of the metathesis of two moles of n-hexane.