title: Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand.
abstract: The platinum(0) alkyne complexes [Pt(L)(η(2)-PhC[triple bond, length as m-dash]CPh)] 1-4 were synthesized by reactions of [Pt(cod)2] with diphenylacetylene and a phosphine ligand precursor (1: L = dcpe, 2: L = xantphos, 3: L = κ(2)-(P,N)-iPr2PC3H6NMe2, 4: L = κ(2)-(P,N)-iPr2PC2H4NMe2). Treatment of 1 or 4 with NFSI gave the complexes [Pt(F){N(SO2Ph)2}(dcpe)] (5) and [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (8), whereas the reactivity of 2 and 3 towards NFSI led to product mixtures. The compounds [Pt(F){N(SO2Ph)2}(xantphos)] (6a) as well as [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (7a) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (7b) were clearly identified. Ligand exchange reactions at 8 resulted in the formation of the β-fluorovinyl platinum(ii) complexes [Pt(PhC[double bond, length as m-dash]CFPh){OC(O)CF3}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (9), [Pt(PhC[double bond, length as m-dash]CFPh)(FHF){κ(2)-(P,N)-iPr2PC2H4NMe2}] (10) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (11). Treatment of 8 with dihydrogen yielded the fluorinated olefin (Z)-(1-fluoroethene-1,2-diyl)dibenzene and [Pt{N(SO2Ph)2}(H){κ(2)-(P,N)-iPr2PC2H4NMe2}] (12).
authors: Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Straße 2, D-12489 Berlin, Germany. thomas.braun@chemie.hu-berlin.de.
authors: Josefine
authors: J
authors: Berger
authors: Thomas
authors: T
authors: Braun
authors: Roy
authors: R
authors: Herrmann
authors: Beatrice
authors: B
authors: Braun